TWI748499B - Substrate processing method and substrtae processing apparatus - Google Patents

Abstract

The substrate processing method of the present invention includes: a processing liquid supply step of supplying the processing liquid to the surface of a substrate; a processing film forming step of curing or hardening the processing liquid on the surface of the substrate to form and hold the substrate A treatment film for removing an object existing on the surface; and a removing step of removing the treatment film from the substrate while maintaining the removal object in the treatment film by supplying a removal liquid to the surface of the substrate的surface removal. The treatment liquid contains a dissolving component that dissolves at least one of the surface layer of the substrate and the removal target as a dissolution target. The process liquid supply step includes a dissolution step of locally dissolving the dissolution target by the dissolving component in the process liquid supplied to the surface of the substrate.

Description

Substrate processing method and substrate processing device

The present invention relates to a substrate processing method and substrate processing apparatus for processing substrates. The substrates to be processed include, for example, semiconductor wafers, substrates for liquid crystal display devices, organic EL (Electroluminescence, electroluminescence) display devices and other FPD (Flat Panel Display) substrates, substrates for optical disks, substrates for magnetic disks, Substrates for magneto-optical discs, photomasks, ceramic substrates, and solar cell substrates.

In the manufacturing process of a semiconductor device, in order to remove various contaminants attached to the substrate, residues such as processing liquids or resists used in the pre-steps, or various particles (hereinafter sometimes collectively referred to as "removal objects"), And implement the cleaning step.

In the cleaning step, generally, by supplying a cleaning liquid such as DIW (Deionized Water) to the substrate, the physical action of the cleaning liquid is used to remove the object to be removed, or by causing a chemical reaction with the object to be removed The chemical solution is supplied to the substrate to chemically remove the object to be removed.

However, the miniaturization and complication of the uneven pattern formed on the substrate has progressed. Therefore, it is not easy to remove the object to be removed with a cleaning solution or a chemical solution while suppressing damage to the uneven pattern.

Therefore, there is proposed a method of supplying a top coating liquid containing volatile components to a substrate, forming a top coating film by volatilization of the volatile components, and removing the top coating film (see Patent Document 1).

In this method, the top coating liquid undergoes volume shrinkage while curing or hardening to form a top coating film. Thereby, the removal object is separated from the substrate. In addition, the top coating film is dissolved and removed from the substrate with the removal liquid. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 6279037

[The problem to be solved by the invention]

In the substrate processing method described in Patent Document 1, the top coating film is dissolved on the substrate. Therefore, the removal target on the substrate may fall off from the top coating film and the removal target that has fallen off may adhere to the substrate again. Therefore, there is a possibility that the removal target cannot be efficiently removed from the substrate.

Therefore, one of the objects of the present invention is to provide a substrate processing method and a substrate processing apparatus that can efficiently remove the removal target existing on the surface of the substrate. [Technical means to solve the problem]

One embodiment of the present invention provides a substrate processing method, which includes: a processing liquid supply step, which supplies the processing liquid to the surface of the substrate; and a processing film forming step, which solidifies or solidifies the processing liquid on the surface of the substrate. Hardening to form a treatment film that holds the removal object existing on the surface of the substrate; and a removal step of supplying a removal liquid to the surface of the substrate while maintaining the treatment film with the removal object The above-mentioned treatment film is removed from the surface of the above-mentioned substrate. The treatment liquid contains a dissolving component that dissolves at least one of the surface layer of the substrate and the removal target as a dissolution target. In addition, the processing liquid supply step includes a dissolution step in which the dissolution target is partially dissolved by the dissolved component in the processing liquid supplied to the surface of the substrate.

According to this method, the dissolution target (at least one of the surface layer of the substrate and the removal target) is partially dissolved by the dissolving component contained in the treatment liquid. Therefore, by performing the processing liquid supply step, the processing liquid easily enters between the object to be removed and the surface of the substrate. In the process film forming step, if the process liquid is cured or hardened in a state where the process liquid has entered between the removal object and the surface of the substrate, a part of the process film is formed between the removal object and the surface of the substrate. Therefore, in the removal step, the treatment film is removed from the surface of the substrate while holding the object to be removed with sufficient holding force. As a result, the removal target can be efficiently removed from the surface of the substrate.

However, different from the above method, after supplying the solution containing the dissolved components to the substrate, the solution is washed away with the rinse solution, and then the processing film forming solution required to form the processing film is supplied to the substrate. A plurality of liquids are sequentially supplied to the surface of the substrate. Therefore, there is a possibility that the removal object once separated from the surface of the substrate by the dissolving liquid will adhere to the surface of the substrate again before being held in the processing film.

On the other hand, if the processing liquid containing the dissolved component is supplied to the substrate, and the processing liquid is cured or hardened to form the processing film, the processing film can be formed without replacing the processing liquid with another liquid. Therefore, the treatment film can be formed quickly after dissolving the object to be dissolved. Therefore, the treatment film can be formed while maintaining the state in which the removal target has been separated from the surface of the substrate.

In one embodiment of the present invention, the process film forming step includes a dissolution inhibiting step of curing or hardening the process liquid to inhibit the dissolution of the dissolution target by the dissolving component. Therefore, excessive dissolution of the dissolution target based on the dissolving component can be avoided.

In one embodiment of the present invention, the object to be dissolved includes at least the surface layer of the substrate. In addition, the dissolution inhibiting step includes the step of dissolving the surface layer of the substrate by the dissolving component in the treatment film near the contact interface between the treatment film and the substrate.

Therefore, the dissolved components in the processing film near the contact interface between the processing film and the substrate are consumed. The treatment film is formed by curing or hardening the treatment liquid, and therefore, the dissolved components in the treatment film are not easily diffused. Therefore, with the consumption of the dissolved components in the processing film near the contact interface between the processing film and the substrate, the dissolution of the surface layer of the substrate based on the dissolved components in the processing film is suppressed.

Furthermore, not only when the liquid film of the treatment liquid exists on the surface of the substrate, but also after the treatment film is formed, the surface layer of the substrate is dissolved by the dissolving component. Therefore, the adhesion between the processing film and the substrate can be reduced. Thereby, in the removing step after the processing film forming step, the processing film is easily peeled off from the surface of the substrate. That is, it is possible to efficiently remove the processing film in the state where the object to be removed is maintained from the surface of the substrate.

In one embodiment of the present invention, the object to be dissolved includes at least the surface layer of the substrate. In addition, the dissolution inhibiting step includes the step of dissolving the surface layer of the substrate by using the dissolving component in the treatment film to form a gap between the treatment film and the surface of the substrate.

According to this method, a gap is formed between the processing film and the surface of the substrate by dissolving the surface layer of the substrate. The treatment film is formed by curing or hardening the treatment liquid, and therefore has lower fluidity than the treatment liquid. Therefore, the gap formed between the processing film and the surface of the substrate is maintained without being buried by the processing film. Therefore, in the removal step after the treatment film formation step, the removal liquid easily enters the gap between the treatment film and the surface of the substrate. Thereby, it is possible to efficiently remove the processing film in the state of the object to be removed from the surface of the substrate.

In one embodiment of the present invention, the treatment liquid has a solute and a solvent that dissolves the solute. The solute has the above-mentioned soluble component, a highly soluble component, and a low-soluble component that is less soluble in the removal liquid than the above-mentioned highly soluble component. The process film forming step includes a process of forming the process film having the high solubility component in a solid state, the low solubility component in a solid state, and the dissolved component in a solid state. In addition, the removal step includes a step of selectively dissolving the highly soluble component in the solid state in the treatment film in the removal liquid.

According to this method, the removal liquid is used to selectively dissolve the highly soluble components in the solid state in the treatment membrane. "Selectively dissolving highly soluble components in a solid state" does not mean only dissolving highly soluble components in a solid state. The meaning of "selectively dissolving the high solubility components in the solid state" means to slightly dissolve the low solubility components in the solid state, but dissolve most of the high solubility components in the solid state.

Therefore, by dissolving the highly soluble component in the solid state in the removal liquid, the removal liquid can act on the contact interface between the processing film and the substrate. On the other hand, the low-solubility components in the treatment film do not dissolve but are maintained in a solid state. Therefore, it is possible to make the removal liquid act on the contact interface between the low-solubility component in the solid state and the substrate while maintaining the object to be removed by the low-solubility component in the solid state. As a result, the processing film can be quickly removed from the surface of the substrate, and the object to be removed can be efficiently removed from the surface of the substrate together with the processing film.

In one embodiment of the present invention, the removal object existing on the surface of the substrate is chemically bonded to the surface of the substrate. "Chemical bonding between the surface of the object to be removed and the substrate" means that the molecules or atoms constituting the object to be removed and the molecules or atoms constituting the surface of the substrate are bonded by covalent bonds, ionic bonds, metal bonds, etc.

In order to separate the removal object held in the processing film from the surface of the substrate, it can be considered that the physical force (kinetic energy) of the removal object that the self-removing liquid acts on the removal object is increased by supplying a large flow of removal liquid to the surface of the substrate. method. However, when the removal target is chemically bonded to the surface of the substrate, even if the removal target is held by the processing film and the physical force received by the removal fluid increases, it is difficult to remove the target only by the physical force of the removal fluid The material is separated from the surface of the substrate.

Therefore, if at least one of the surface layer of the substrate or the object to be removed is dissolved by the dissolved component contained in the treatment liquid, the object to be removed can be separated from the surface of the substrate regardless of the bond strength between the object to be removed and the surface of the substrate . Therefore, even when the removal target is chemically bonded to the surface of the substrate, the removal target can be efficiently removed from the surface of the substrate.

In one embodiment of the present invention, the object to be dissolved includes at least the object to be removed. In addition, the removal target includes a removal target film covering at least a part of the surface of the substrate. For example, there is a case where a film-like residue (removal target film) covering at least a part of the surface of the substrate is generated on the surface of the substrate after dry etching. Different from this method, when a processing film is formed from a processing solution that does not have a dissolved component, it is difficult for the processing solution to enter between the removal target film and the surface of the substrate in the portion of the substrate surface covered by the removal target film.

Therefore, if the removal target film can be partially dissolved in the dissolved component in the treatment liquid, the treatment liquid can easily enter between the removal target film and the surface of the substrate. Furthermore, if the removal target film can be split by the dissolved components in the treatment liquid, the treatment solution can be more efficiently entered between the surface of the removal target film and the substrate through the gap between the split films. between.

In one embodiment of the present invention, the object to be dissolved includes at least the object to be removed. The above-mentioned removal object is a residue generated by chemical mechanical polishing (CMP: Chemical Mechanical Polishing). There are cases where the surface of the substrate after chemical mechanical polishing has the same degree of solubility for dissolved components as the surface layer of the substrate. Therefore, if the surface layer of the substrate can be dissolved by the dissolving component, the part near the surface of the object to be removed will also be dissolved. Therefore, it is easy for the treatment liquid to enter between the object to be removed and the surface of the substrate.

Another embodiment of the present invention provides a substrate processing apparatus including: a processing liquid supply unit that supplies the processing liquid to the surface of a substrate; and a processing film forming unit that solidifies or hardens the processing liquid on the surface of the substrate Forming a treatment film that holds the removal object existing on the surface of the substrate; a removal liquid supply unit that removes the treatment film from the surface of the substrate by supplying a removal liquid to the surface of the substrate; and a controller, It controls the processing liquid supply unit, the processing film forming unit, and the removal liquid supply unit.

The controller is programmed to execute the following steps: a processing liquid supply step, which supplies the processing liquid from the processing liquid supply unit toward the surface of the substrate; The treatment liquid on the surface is solidified or hardened to form the treatment film on the upper surface of the substrate; and the removing step is performed by supplying the removal liquid from the removal liquid supply unit toward the surface of the substrate to cause The process film is removed from the surface of the substrate in a state where the object to be removed is held in the process film. The treatment liquid contains a dissolving component that dissolves at least one of the surface layer of the substrate and the removal target as a dissolution target. In addition, the controller is programmed to perform a dissolving step in the processing liquid supply step, and the dissolution step is to partially dissolve the dissolution target by the dissolving component in the processing liquid supplied to the surface of the substrate.

According to this device, the dissolution target (at least one of the surface layer of the substrate and the removal target) is partially dissolved by the dissolving component contained in the treatment liquid. Therefore, by performing the processing liquid supply step, the processing liquid easily enters between the object to be removed and the surface of the substrate. In the process film forming step, if the process liquid is cured or hardened in a state where the process liquid has entered between the removal object and the surface of the substrate, a part of the process film is formed between the removal object and the surface of the substrate. Therefore, in the removal step, the treatment film is removed from the surface of the substrate while holding the object to be removed with sufficient holding force. As a result, the removal target can be efficiently removed from the surface of the substrate.

However, unlike the above-mentioned device, when the solution containing the dissolved components is supplied to the substrate, the solution is washed away by the rinse solution, and then the treatment film forming solution required to form the treatment film is supplied to the substrate. A plurality of liquids are sequentially supplied to the surface of the substrate. Therefore, there is a possibility that the removal object once separated from the surface of the substrate by the dissolving liquid will adhere to the surface of the substrate again before being held in the processing film.

On the other hand, if the processing liquid containing the dissolved component is supplied to the substrate, and the processing liquid is cured or hardened to form the processing film, the processing film can be formed without replacing the processing liquid with another liquid. Therefore, the treatment film can be formed quickly after dissolving the object to be dissolved. Therefore, the treatment film can be formed while maintaining the state in which the removal target has been separated from the surface of the substrate.

In another embodiment of the present invention, the above-mentioned controller is programmed in such a way that, in the above-mentioned processing film forming step, a dissolution inhibiting step is performed by curing or hardening the above-mentioned processing liquid to inhibit utilization. The dissolving component dissolves the dissolution target. Therefore, excessive dissolution of the dissolution target based on the dissolving component can be avoided.

In another embodiment of the present invention, the object to be dissolved includes at least the surface layer of the substrate. In addition, the controller is programmed to perform the step of dissolving the surface layer of the substrate by the dissolving component in the processing film near the contact interface between the processing film and the substrate in the dissolution inhibiting step.

Therefore, the dissolved components in the processing film near the contact interface between the processing film and the substrate are consumed. The treatment film is formed by curing or hardening the treatment liquid, and therefore, the dissolved components in the treatment film are not easily diffused. Therefore, with the consumption of the dissolved components in the processing film near the contact interface between the processing film and the substrate, the dissolution of the surface layer of the substrate based on the dissolved components in the processing film is suppressed.

Furthermore, not only when the liquid film of the treatment liquid exists on the surface of the substrate, but also after the treatment film is formed, the surface layer of the substrate is dissolved by the dissolving component. Therefore, the adhesion between the processing film and the substrate can be reduced. Thereby, in the removing step after the processing film forming step, the processing film is easily peeled off from the surface of the substrate. That is, it is possible to efficiently remove the processing film in the state where the object to be removed is maintained from the surface of the substrate.

In another embodiment of the present invention, the object to be dissolved includes at least the surface layer of the substrate. In addition, the controller is programmed to perform the step of forming a gap between the processing film and the surface of the substrate by dissolving the surface layer of the substrate by using the dissolving component in the processing film in the dissolution suppression step.

According to this device, by dissolving the surface layer of the substrate, a gap is formed between the processing film and the surface of the substrate. The treatment film is formed by curing or hardening the treatment liquid, and therefore has lower fluidity than the treatment liquid. Therefore, the gap formed between the processing film and the surface of the substrate is maintained without being buried by the processing film. Therefore, in the removal step after the treatment film formation step, the removal liquid easily enters the gap between the treatment film and the surface of the substrate. Thereby, it is possible to efficiently remove the processing film in the state of the object to be removed from the surface of the substrate.

In another embodiment of the present invention, the treatment liquid has a solute and a solvent that dissolves the solute. The solute has the above-mentioned soluble component, a highly soluble component, and a low-soluble component that is less soluble in the removal liquid than the above-mentioned highly soluble component. In addition, the controller is programmed to form, in the process film forming step, the process film having the high solubility component in a solid state, the low solubility component in a solid state, and the dissolved component in a solid state, and in the removal step In the process, the highly soluble component in the solid state in the treatment membrane is selectively dissolved in the removal liquid.

According to this device, the removal liquid is used to selectively dissolve the highly soluble components in the solid state in the treatment membrane. Therefore, by dissolving the highly soluble component in the solid state in the removal liquid, the removal liquid can act on the contact interface between the processing film and the substrate. On the other hand, the low-solubility components in the treatment film do not dissolve but are maintained in a solid state. Therefore, it is possible to make the removal liquid act on the contact interface between the low-solubility component in the solid state and the substrate while maintaining the object to be removed by the low-solubility component in the solid state. As a result, the processing film can be quickly removed from the surface of the substrate, and the object to be removed can be efficiently removed from the surface of the substrate together with the processing film.

In another embodiment of the present invention, the removal object existing on the surface of the substrate is chemically bonded to the surface of the substrate. If at least one of the surface layer of the substrate or the object to be removed is dissolved by the dissolving component contained in the treatment liquid, the object to be removed can be separated from the surface of the substrate regardless of the bond strength between the object to be removed and the surface of the substrate. Therefore, even when the removal target is chemically bonded to the surface of the substrate, the removal target can be efficiently removed from the surface of the substrate.

In another embodiment of the present invention, the object to be dissolved includes at least the object to be removed. In addition, the removal target includes a removal target film covering at least a part of the surface of the substrate. As described above, for example, a film-like residue (film to be removed) covering at least a part of the surface of the substrate may be generated on the surface of the substrate after dry etching. Unlike this device, when a processing film is formed from a processing liquid that does not have a dissolved component, the processing liquid hardly enters between the surface of the substrate and the film to be removed in the part of the surface of the substrate covered by the film to be removed.

Therefore, if the removal target film can be partially dissolved in the dissolved component in the treatment liquid, the treatment liquid can easily enter between the removal target film and the surface of the substrate. Furthermore, if the dissolved components in the treatment liquid can be used to split the removal target film, the treatment solution can be more efficiently entered between the film of the removal target film and the surface of the substrate through the gap between the split films. .

In another embodiment of the present invention, the object to be dissolved includes at least the object to be removed. The above-mentioned removal object is the residue generated by CMP. As described above, the surface of the substrate after CMP may have the same degree of solubility for dissolved components as the surface layer of the substrate. Therefore, if the surface layer of the substrate can be dissolved by the dissolving component, the part near the surface of the object to be removed will also be dissolved. Therefore, it is easy for the treatment liquid to enter between the object to be removed and the surface of the substrate.

The above or further objects, features, and effects of the present invention will be clarified by the description of the embodiments described below with reference to the accompanying drawings.

＜Constitution of substrate processing equipment＞

FIG. 1 is a schematic plan view showing the layout of a substrate processing apparatus 1 according to an embodiment of the present invention.

The substrate processing device 1 is a single-chip device that processes substrates W such as silicon wafers one by one. In this embodiment, the substrate W is a disc-shaped substrate.

The substrate processing apparatus 1 includes: a plurality of processing units 2 that use fluid to process a substrate W; a loading port LP for placing a carrier C that accommodates a plurality of substrates W processed by the processing unit 2; a transport robot IR and CR, which transfers the substrate W between the load port LP and the processing unit 2; and the controller 3, which controls the substrate processing apparatus 1.

The transfer robot IR transfers the substrate W between the carrier C and the transfer robot CR. The transfer robot CR transfers the substrate W between the transfer robot IR and the processing unit 2. The plural processing units 2 have the same configuration, for example. Details will be described below. The processing fluid supplied to the substrate W in the processing unit 2 includes a rinse liquid, a processing liquid, a removal liquid, a processing film residue removal liquid, a heat medium, an inert gas, and the like.

Each processing unit 2 includes a chamber 4 and a processing cup 7 arranged in the chamber 4, and the substrate W is processed in the processing cup 7. The chamber 4 is formed with an entrance (not shown) for carrying the substrate W in or carrying out the substrate W by the transport robot CR. A baffle unit (not shown) that opens and closes the entrance and exit is arranged in the chamber 4.

FIG. 2 is a schematic diagram for explaining a configuration example of the processing unit 2. The processing unit 2 includes a rotating chuck 5, an opposing member 6, a processing cup 7, a first moving nozzle 9, a second moving nozzle 10, a center nozzle 11, and a bottom surface nozzle 12.

While holding the substrate W horizontally, the rotating chuck 5 rotates the substrate W around the vertical rotation axis A1 (vertical axis) passing through the center of the substrate W. The rotating chuck 5 includes a plurality of chuck pins 20, a rotating base 21, a rotating shaft 22 and a rotating motor 23.

The rotating base 21 has a circular plate shape along the horizontal direction. On the upper surface of the rotating base 21, a plurality of chuck pins 20 for holding the peripheral edge of the substrate W are arranged at intervals in the circumferential direction of the rotating base 21. The spin base 21 and the plurality of chuck pins 20 constitute a substrate holding unit that holds the substrate W horizontally. The substrate holding unit is also called a substrate holder.

The rotation shaft 22 extends in the vertical direction along the rotation axis A1. The upper end of the rotating shaft 22 is coupled to the center of the lower surface of the rotating base 21. The rotating motor 23 applies a rotating force to the rotating shaft 22. By rotating the rotating shaft 22 with the rotating motor 23, the rotating base 21 is rotated. Thereby, the substrate W is rotated about the rotation axis A1. The rotation motor 23 is an example of a substrate rotating unit that rotates the substrate W around the rotation axis A1.

The opposing member 6 opposes the substrate W held by the spin chuck 5 from above. The opposing member 6 is formed in a circular plate shape having a diameter substantially the same as that of the substrate W or a diameter greater than that. The opposing member 6 has an opposing surface 6a opposing the upper surface of the substrate W (the surface on the upper side). The facing surface 6a is arranged along a substantially horizontal plane above the rotating chuck 5.

A hollow shaft 60 is fixed to the opposing member 6 on the opposite side of the opposing surface 6a. In a portion of the opposing member 6 that overlaps the rotation axis A1 in a plan view, a communication hole 6b that penetrates the opposing member 6 up and down and communicates with the internal space 60a of the hollow shaft 60 is formed.

The facing member 6 shields the atmosphere in the space between the facing surface 6a and the upper surface of the substrate W from the atmosphere outside the space. Therefore, the facing member 6 is also called a blocking plate.

The processing unit 2 further includes a facing member lifting unit 61 that drives the facing member 6 to lift. The facing member lifting unit 61 can position the facing member 6 at any position (height) from a lower position to an upper position. The so-called lower position is within the movable range of the opposing member 6 and the position where the opposing surface 6a and the substrate W are closest. The so-called upper position is within the movable range of the facing member 6, and the position where the facing surface 6a is farthest from the substrate W.

The facing member lifting unit 61 includes, for example, a ball screw mechanism (not shown), which is coupled to a supporting member (not shown) that supports the hollow shaft 60, and an electric motor (not shown), which gives the ball screw mechanism Driving force. The facing member lifting unit 61 is also referred to as a facing member lifter (blocking plate lifter).

The processing cup 7 includes: a plurality of shields 71, which receive the liquid splashed to the outside from the substrate W held on the rotating chuck 5; Liquid; and a cylindrical outer wall member 73, which surrounds a plurality of shields 71 and a plurality of cups 72.

In this embodiment, an example is shown in which two shields 71 (first shield 71A and second shield 71B) and two cups 72 (first cup 72A and second cup 72B) are provided.

Each of the first cup 72A and the second cup 72B has the shape of an upwardly open annular groove.

The first shield 71A is arranged to surround the rotating base 21. The second shield 71B is arranged to surround the rotation base 21 on the outer side in the rotation radial direction of the substrate W than the first shield 71A.

Each of the first shield 71A and the second shield 71B has a substantially cylindrical shape, and the upper end of each shield 71 is inclined inwardly so as to face the rotating base 21.

The first cup 72A receives the liquid guided downward by the first shield 71A. The second cup 72B is formed integrally with the first shield 71A, and receives the liquid guided downward by the second shield 71B.

The processing unit 2 includes a shield raising and lowering unit 74 that individually raises and lowers the first shield 71A and the second shield 71B. The shield raising and lowering unit 74 raises and lowers the first shield 71A between the lower position and the upper position. The shield raising and lowering unit 74 raises and lowers the second shield 71B between the lower position and the upper position.

When the first shield 71A and the second shield 71B are both in the upper position, the liquid splashed from the substrate W is caught by the first shield 71A. When the first shield 71A is in the lower position and the second shield 71B is in the upper position, the liquid splashed from the substrate W is caught by the second shield 71B.

The shield raising and lowering unit 74 includes, for example, a first ball screw mechanism (not shown), which is coupled to the first shield 71A, a first motor (not shown), which imparts a driving force to the first ball screw mechanism, and a second A ball screw mechanism (not shown), which is coupled to the second shield 71B, and a second motor (not shown), which imparts a driving force to the second ball screw mechanism. The shield lift unit 74 is also called a shield lifter.

The first moving nozzle 9 is an example of a processing liquid nozzle (processing liquid supply unit) that supplies (discharges) the processing liquid toward the upper surface of the substrate W held by the spin chuck 5.

The first moving nozzle 9 is moved in the horizontal direction and the vertical direction by the first nozzle moving unit 36. The first moving nozzle 9 can move between the center position and the home position (retracted position) in the horizontal direction. When the first moving nozzle 9 is at the center position, it faces the center of rotation of the upper surface of the substrate W. The rotation center of the upper surface of the substrate W is the intersection position of the upper surface of the substrate W with the rotation axis A1. When the first moving nozzle 9 is at the home position, it is not opposed to the upper surface of the substrate W, but is located outside the processing cup 7 in a plan view. The first moving nozzle 9 can approach the upper surface of the substrate W or retract upward from the upper surface of the substrate W by moving in the vertical direction.

The first nozzle moving unit 36 includes, for example, a rotating shaft (not shown) along the vertical direction; an arm (not shown) coupled to the rotating shaft and extending horizontally; and a rotating shaft drive unit (not shown) , Which makes the rotating shaft lift or rotate.

The rotating shaft drive unit swings the arm by rotating the rotating shaft around a vertical rotation axis. Furthermore, the rotating shaft drive unit moves the arm up and down by raising and lowering the rotating shaft in the vertical direction. The first moving nozzle 9 is fixed to the arm. Corresponding to the swinging and raising/lowering of the arm, the first moving nozzle 9 moves in the horizontal direction and the vertical direction.

The first moving nozzle 9 is connected to a processing liquid pipe 40 that guides the processing liquid. When the processing liquid valve 50 installed in the processing liquid piping 40 is opened, the processing liquid is ejected downward from the first moving nozzle 9 in a continuous flow.

The processing liquid ejected from the first moving nozzle 9 contains a solute and a solvent. The treatment liquid is solidified or hardened by volatilization (evaporation) of at least a part of the solvent. The processing liquid is cured or hardened on the substrate W to form a processing film that retains the removal target such as particles present on the substrate W. The object to be removed is, for example, foreign matter attached to the surface of the substrate W after dry etching or CMP.

Here, "solidification" refers to, for example, the solidification of the solute by forces acting between molecules or atoms along with the volatilization of the solvent. For example, "hardening" refers to the solidification of the solute through chemical changes such as polymerization or crosslinking. Therefore, "solidification or hardening" means that the solute "solidifies" due to various factors.

The solute contained in the treatment liquid ejected from the first moving nozzle 9 includes a dissolved component, a low-soluble component, a high-soluble component, and an anti-corrosion component.

The dissolving component is a component that dissolves at least one of the surface layer of the substrate W and the object to be removed as the object to be dissolved. The surface layer of the substrate W refers to the part near the surface of the substrate W. The surface layer of the substrate W after dry etching is formed of, for example, a Low-k (low dielectric constant) film, TiN, SiO ₂ , Si, SiN, SiC, and polysilicon. The surface layer of the substrate W after CMP is formed of, for example, metal, Si, SiO ₂ , SiC, GaN, and the like. Examples of the metal forming the surface layer of the substrate W after CMP include aluminum, tungsten, copper, cobalt, ruthenium, molybdenum, and the like. The dissolving component is, for example, an acid or an alkali that dissolves the object to be removed. The surface layer of the substrate W may also include a natural oxide film.

The anti-corrosion component is a component used to prevent the corrosion of metals. Therefore, when a metal layer is included in the surface layer of the substrate W, it is preferable that the solute contained in the treatment liquid sprayed from the first moving nozzle 9 contains an anti-corrosion component. The details will be described below, and the anti-corrosion component is, for example, BTA (benzotriazole).

The low-solubility component and the high-solubility component can use substances with different solubility for the removal liquid. The low-solubility component contained in the treatment liquid sprayed from the first moving nozzle 9 is, for example, novolac. The highly soluble component contained in the processing liquid ejected from the first moving nozzle 9 is, for example, 2,2-bis(4-hydroxyphenyl)propane.

The solvent contained in the processing liquid ejected from the first moving nozzle 9 may be a liquid that dissolves a low-soluble component, a high-soluble component, a dissolved component, and an anticorrosive component. The solvent contained in the treatment liquid is preferably a liquid having compatibility (miscible) with the removal liquid. The so-called compatibility refers to the properties of two liquids that are dissolved and mixed with each other.

The details of the solvent, low-solubility component, high-solubility component, soluble component, and anti-corrosion component contained in the treatment liquid sprayed from the first moving nozzle 9 will be described below.

The second moving nozzle 10 is an example of a removing liquid nozzle (removing liquid supply unit) that supplies (discharges) removal liquid such as pure water in a continuous flow toward the upper surface of the substrate W held on the spin chuck 5. The removing liquid is a liquid used to remove the treatment film in the state of the object to be removed from the upper surface of the substrate W.

The second moving nozzle 10 is moved in the horizontal direction and the vertical direction by the second nozzle moving unit 37. The second moving nozzle 10 can move between the center position and the home position (retracted position) in the horizontal direction.

When the second moving nozzle 10 is located at the center position, it faces the center of rotation of the upper surface of the substrate W. When the second moving nozzle 10 is at the home position, it is not opposed to the upper surface of the substrate W, but is located on the outer side of the processing cup 7 in a plan view. The second moving nozzle 10 can approach the upper surface of the substrate W or retract upward from the upper surface of the substrate W by moving in the vertical direction.

The second nozzle moving unit 37 has the same configuration as the first nozzle moving unit 36. That is, the second nozzle moving unit 37 includes, for example, a rotating shaft (not shown) along the vertical direction; an arm (not shown) coupled to the rotating shaft and the second moving nozzle 10 and extending horizontally; and rotating A shaft drive unit (not shown), which lifts or rotates the rotating shaft.

As the removal liquid ejected from the second moving nozzle 10, a liquid which is easier to dissolve the highly soluble components contained in the solute of the processing liquid than the low soluble components contained in the solute of the processing liquid is used. The removal liquid sprayed from the second moving nozzle 10 is, for example, pure water (preferably DIW). The removal liquid is not limited to pure water, and may be an alkaline aqueous solution (alkaline liquid), neutral and acidic aqueous solution (non-alkaline aqueous solution). Specific examples of alkaline aqueous solutions include ammonia, SC1 (ammonia-hydrogen peroxide mixture), TMAH (tetramethylammonium hydroxide) aqueous solution, and choline aqueous solution, and any of them. A combination.

The second moving nozzle 10 is connected to a removing liquid pipe 41 that guides the removing liquid to the upper side of the second moving nozzle 10. When the removal liquid valve 51 on the upper side of the upper removal liquid piping 41 is opened, the removal liquid is sprayed downward from the discharge port of the second moving nozzle 10 in a continuous flow.

The central nozzle 11 is accommodated in the inner space 60 a of the hollow shaft 60 of the facing member 6. The ejection port 11a provided at the front end of the central nozzle 11 faces the central area of the upper surface of the substrate W from above. The central area of the upper surface of the substrate W refers to the area on the upper surface of the substrate W that includes the center of rotation of the substrate W and its surroundings.

The central nozzle 11 includes a plurality of tubes (the first tube 31, the second tube 32, and the third tube 33) that eject fluid downward, and a cylindrical casing 30 that surrounds the plurality of tubes. The plurality of tubes and the housing 30 extend in the vertical direction along the rotation axis A1. The ejection port 11a of the central nozzle 11 is also the ejection port of the first pipe 31, the ejection port of the second pipe 32, and the ejection port of the third pipe 33.

The first pipe 31 (central nozzle 11) is an example of a rinse liquid supply unit that supplies a rinse liquid such as DIW to the upper surface of the substrate W. The second pipe 32 (central nozzle 11) is an example of an organic solvent supply unit that supplies a residue removal liquid of a treatment film such as IPA (Isopropyl Alcohol) to the upper surface of the substrate W. The third pipe 33 (central nozzle 11) is an example of a gas supply unit that supplies gas such as nitrogen gas between the upper surface of the substrate W and the facing surface 6a of the facing member 6.

The first pipe 31 is connected to a rinsing liquid piping 42 that guides the rinsing liquid to the upper side of the first pipe 31. When the flushing liquid valve 52 installed on the upper flushing liquid piping 42 is opened, the flushing liquid is sprayed from the first tube 31 (central nozzle 11) toward the central area of the upper surface of the substrate W in a continuous flow.

Examples of the rinse solution include DIW, carbonated water, electrolyzed ionized water, hydrochloric acid water with a dilution concentration (for example, about 1 ppm to 100 ppm), ammonia water with a dilution concentration (for example, about 1 ppm to 100 ppm), and reduced water (hydrogen). Water) and so on.

The second pipe 32 is connected to a treatment film residue removal liquid pipe 43 that guides the treatment film residue removal liquid to the second pipe 32. When the treatment membrane residue removal liquid valve 53 installed in the treatment membrane residue removal liquid pipe 43 is opened, the treatment membrane residue removal liquid flows continuously from the second pipe 32 (central nozzle 11) toward the central area of the upper surface of the substrate W. The form squirts.

The treatment film residue removal liquid sprayed from the second pipe 32 is a liquid used to remove the treatment film residues that have been removed from the upper surface of the substrate W by the removal liquid. The treatment membrane residue removal liquid is preferably a liquid with higher volatility than the rinse liquid. The treatment film residue removal liquid sprayed from the second pipe 32 is preferably compatible with the rinse liquid.

The treatment film residue removal liquid ejected from the second pipe 32 is, for example, an organic solvent. The organic solvent sprayed from the second pipe 32 includes at least 1 of IPA, HFE (hydrofluoroether), methanol, ethanol, acetone, PGEE (propylene glycol monoethyl ether), and trans-1,2-dichloroethylene Kind of liquid and so on.

In addition, the organic solvent sprayed from the second tube 32 does not need to be composed only of monomer components, and may be a liquid mixed with other components. For example, it can be a mixture of IPA and DIW, or a mixture of IPA and HFE.

The third pipe 33 is connected to a gas pipe 44 that guides the gas to the third pipe 33. When the gas valve 54 interposed in the gas pipe 44 is opened, the gas is ejected in a continuous flow downward from the third pipe 33 (the central nozzle 11).

The gas ejected from the third pipe 33 is, for example, an inert gas _{such as nitrogen (N 2 ).} The gas ejected from the third pipe 33 may also be air. The so-called inert gas is not limited to nitrogen, and refers to a gas that is inert with respect to the upper surface of the substrate W or the pattern formed on the upper surface of the substrate W. As an example of the inert gas, in addition to nitrogen, rare gases such as argon can be cited.

The lower surface nozzle 12 is inserted into the through hole 21 a opened in the center of the upper surface of the spin base 21. The ejection port 12a of the lower surface nozzle 12 is exposed from the upper surface of the rotating base 21. The ejection port 12a of the lower surface nozzle 12 faces the central area of the lower surface (the surface of the lower side) of the substrate W from below. The central area of the lower surface of the substrate W refers to the area on the lower surface of the substrate W that contains the center of rotation of the substrate W.

One end of a common pipe 80 that guides the flushing liquid, the removal liquid, and the heat medium to the lower surface nozzle 12 is connected to the lower surface nozzle 12. Connected to the other end of the common pipe 80 is a rinsing liquid piping 81 that guides the rinsing liquid to the lower side of the common piping 80, a removal liquid piping 82 that guides the removal liquid to the lower side of the common piping 80, and a heat medium to the common piping 80. The heat medium piping 83.

When the flushing liquid valve 86 installed under the lower flushing liquid piping 81 is opened, the flushing liquid is sprayed from the lower surface nozzle 12 toward the central area of the lower surface of the substrate W in a continuous flow. When the removal liquid valve 87 installed under the lower removal liquid piping 82 is opened, the removal liquid is sprayed from the lower surface nozzle 12 toward the center area of the lower surface of the substrate W in a continuous flow. When the heating medium valve 88 installed in the heating medium pipe 83 is opened, the heating medium is ejected from the lower surface nozzle 12 toward the central area of the lower surface of the substrate W in a continuous flow.

The lower surface nozzle 12 is an example of a lower side rinse liquid supply unit for supplying rinse liquid to the lower surface of the substrate W. In addition, the lower surface nozzle 12 is an example of a removal liquid supply unit that supplies the removal liquid to the lower surface of the substrate W. In addition, the lower surface nozzle 12 is an example of a heat medium supply unit that supplies a heat medium for heating the substrate W to the substrate W. The bottom surface nozzle 12 is also a substrate heating unit that heats the substrate W.

The heat medium ejected from the lower surface nozzle 12 is, for example, a high-temperature DIW whose temperature is higher than room temperature and lower than the boiling point of the solvent contained in the treatment liquid. When the solvent contained in the treatment liquid is IPA, as the heat medium, for example, DIW at 60°C to 80°C is used. The heat medium sprayed from the nozzle 12 on the lower surface is not limited to high-temperature DIW, and can also be high-temperature inert gas or high-temperature air such as high-temperature gas with a temperature higher than room temperature and lower than the boiling point of the solvent contained in the treatment liquid.

FIG. 3 is a block diagram showing the electrical configuration of the main part of the substrate processing apparatus 1. The controller 3 is equipped with a microcomputer, and controls the control object of the substrate processing apparatus 1 according to a specific control program.

Specifically, the controller 3 includes a processor (CPU (Central Processing Unit, Central Processing Unit)) 3A, and a memory 3B storing a control program. The controller 3 is configured to execute various controls for substrate processing by the processor 3A executing a control program.

In particular, the controller 3 controls the transport robot IR, CR, the rotation motor 23, the first nozzle moving unit 36, the second nozzle moving unit 37, the facing member lifting unit 61, the shield lifting unit 74, and the treatment liquid valve. 50. The modes of the upper liquid removal valve 51, the upper washing liquid valve 52, the treatment membrane residue removal liquid valve 53, the gas valve 54, the lower washing liquid valve 86, the lower liquid removing valve 87 and the heating medium valve 88 are programmed. By using the controller 3 to control the valve, it is possible to control whether the treatment fluid is sprayed from the corresponding nozzle or the spray flow rate of the treatment fluid from the corresponding nozzle.

＜An example of substrate processing＞ FIG. 4 is a flowchart for explaining an example of substrate processing performed by the substrate processing apparatus 1. FIG. 4 mainly shows the processing realized by the controller 3 executing the program. 5A to 5H are schematic diagrams for explaining the various steps of the above-mentioned substrate processing.

In the substrate processing performed by the substrate processing apparatus 1, for example, as shown in FIG. 4, the substrate carrying step (step S1), the processing liquid supply step (step S2), the thinning step (step S3), and the solvent evaporation step are sequentially performed as shown in FIG. (Step S4), removal step (step S5), rinse step (step S6), process film residue removal step (step S7), spin drying step (step S8), and substrate unloading step (step S9).

First, the unprocessed substrate W is transferred from the carrier C to the processing unit 2 by the transfer robot IR, CR (refer to FIG. 1), and transferred to the spin chuck 5 (step S1). Thereby, the substrate W is held horizontally by the spin chuck 5 (substrate holding step). When the substrate W is carried in, the facing member 6 is retracted to the upper position.

The holding system of the substrate W by the spin chuck 5 continues until the spin drying step (step S8) ends. The shield raising and lowering unit 74 adjusts the first shield 71A and the second shield 71B in such a manner that at least one shield 71 is located in the upper position during the period from the start of the substrate holding step to the end of the spin drying step (step S8) Height position.

Then, after the transport robot CR is retracted to the outside of the processing unit 2, the processing liquid supply step is started (step S2). In the process liquid supply step, first, the rotating motor 23 rotates the rotating base 21. Thereby, the substrate W held horizontally is rotated (substrate rotation step).

With the opposing member 6 in the upper position, the first nozzle moving unit 36 moves the first moving nozzle 9 to the processing position. The processing position of the first moving nozzle 9 is, for example, a central position. Then, the treatment liquid valve 50 is opened. Thereby, as shown in FIG. 5A, the processing liquid is supplied (discharged) from the first moving nozzle 9 toward the center region of the upper surface of the substrate W in the rotating state (processing liquid supply step, processing liquid discharge step). Thereby, the liquid film 101 of the processing liquid (processing liquid film) is formed on the substrate W (processing liquid film forming step). At least one of the object to be removed on the upper surface of the substrate W and the surface layer of the substrate W is partially dissolved by the dissolving component contained in the treatment liquid (dissolving step).

The treatment liquid is supplied from the first moving nozzle 9 for a specific time, for example, between 2 seconds and 4 seconds. In the processing liquid supply step, the substrate W is rotated at a specific processing liquid rotation speed, for example, 10 rpm to 1500 rpm.

Then, the process film formation step (step S3 and step S4) is performed. In the process film forming step, the process liquid on the substrate W is cured or hardened, and the process film 100 holding the removal target existing on the substrate W is formed on the upper surface of the substrate W (see FIG. 5D).

In the processing film forming step, first, a thinning step of thinning the thickness of the liquid film 101 of the processing liquid on the substrate W (the spin-off step) is performed (step S3). Specifically, the treatment liquid valve 50 is closed. Thereby, the supply of the processing liquid to the substrate W is stopped. Then, the first moving nozzle 9 is moved to the home position by the first nozzle moving unit 36.

As shown in FIG. 5B, in the thinning step, the thickness of the liquid film 101 on the substrate W becomes an appropriate thickness, and the treatment liquid is removed by centrifugal force in a state where the supply of the treatment liquid to the upper surface of the substrate W is stopped. A part is excluded from the upper surface of the substrate W.

After the first moving nozzle 9 is moved to the original position, the facing member 6 is also maintained at the upper position.

In the filming step, the rotating motor 23 changes the rotation speed of the substrate W to a specific filming speed. The filming speed is, for example, 300 rpm to 1500 rpm. The rotation speed of the substrate W can be kept constant in the range of 300 rpm to 1500 rpm, and can also be appropriately changed in the range of 300 rpm to 1500 rpm in the middle of the thin filming step. The thin film forming step is performed for a specific time, for example, 30 seconds.

In the processing film forming step, a solvent evaporation step of partially evaporating (volatizing) a part of the solvent from the liquid film 101 of the processing liquid is performed after the thinning step (step S4). In the solvent evaporation step, the liquid film 101 on the substrate W is heated to evaporate a part of the solvent of the processing liquid on the substrate W.

Specifically, as shown in FIG. 5C, the facing member lifting unit 61 moves the facing member 6 to a close position between the upper position and the lower position. The approaching position may also be the down position. The approaching position is a position where the distance from the upper surface of the substrate W to the facing surface 6a is, for example, 1 mm.

Then, the gas valve 54 is opened. Thereby, gas is supplied to the space between the upper surface of the substrate W (the upper surface of the liquid film 101) and the facing surface 6a of the facing member 6 (gas supply step).

By blowing gas to the liquid film 101 on the substrate W, the evaporation (evaporation) of the solvent in the liquid film 101 is promoted (solvent evaporation step, solvent evaporation promotion step). Therefore, the time required to form the processing film 100 can be shortened. The central nozzle 11 functions as an evaporation unit (evaporation promotion unit) for evaporating the solvent in the treatment liquid.

Furthermore, the heating medium valve 88 is opened. Thereby, the heat medium is supplied (discharged) from the lower surface nozzle 12 toward the central area of the lower surface of the substrate W in the rotating state (heat medium supply step, heat medium discharge step). The heating medium supplied from the bottom surface nozzle 12 to the bottom surface of the substrate W is diffused radially by centrifugal force and spreads over the entire bottom surface of the substrate W. The heating medium is supplied to the substrate W for a specific time, for example, 60 seconds. In the solvent evaporation step, the substrate W is rotated at a specific evaporation speed, for example, 1000 rpm.

By supplying a heat medium to the lower surface of the substrate W, the liquid film 101 on the substrate W is heated through the substrate W. Thereby, the evaporation (evaporation) of the solvent in the liquid film 101 is promoted (solvent evaporation step, solvent evaporation promotion step). Therefore, the time required to form the processing film 100 can be shortened. The lower surface nozzle 12 functions as an evaporation unit (evaporation promotion unit) that evaporates (volatizes) the solvent in the treatment liquid.

By performing the thinning step and the solvent evaporation step, the treatment liquid is solidified or hardened, so that the treatment film 100 is formed on the substrate W as shown in FIG. 5D. In this way, the substrate rotating unit (rotating motor 23), the central nozzle 11, and the lower surface nozzle 12 constitute a solid forming unit (processed film forming unit) that solidifies or hardens the process liquid to form a solid (processed film 100).

In the solvent evaporation step, it is preferable to heat the substrate W in such a way that the temperature of the processing liquid on the substrate W does not reach the boiling point of the solvent. By heating the treatment liquid to a temperature below the boiling point of the solvent, the solvent can be appropriately left in the treatment film 100. Thereby, compared with the case where the solvent does not remain in the treatment film 100, it is easier to dissolve the removal liquid in the treatment film 100 by the interaction between the solvent remaining in the treatment film 100 and the removal liquid in the subsequent removal step. middle.

Then, a removal step of peeling and removing the processing film 100 from the upper surface of the substrate W is performed (step S5). Specifically, the heating medium valve 88 is closed. Thereby, the supply of the heating medium to the lower surface of the substrate W is stopped. Furthermore, the gas valve 54 is closed. Thereby, the gas supply to the space between the facing surface 6a of the facing member 6 and the upper surface of the substrate W is stopped.

Then, the facing member elevating unit 61 moves the facing member 6 to the upper position. With the opposing member 6 in the upper position, the second nozzle moving unit 37 moves the second moving nozzle 10 to the processing position. The processing position of the second moving nozzle 10 is, for example, a central position.

Then, with the second moving nozzle 10 at the processing position, the upper liquid removal valve 51 is opened. Thereby, as shown in FIG. 5E, the removal liquid is supplied (discharged) from the second moving nozzle 10 toward the central area of the upper surface of the substrate W in the rotating state (upper removal liquid supply step, upper removal liquid discharge step). The removal liquid supplied to the upper surface of the substrate W is diffused to the entire upper surface of the substrate W by centrifugal force. In the removal step, the substrate W is rotated at a specific removal rotation speed, for example, 800 rpm.

Simultaneously with the opening of the upper liquid removal valve 51, the lower liquid removal valve 87 is opened. Thereby, the removal liquid is supplied (discharged) from the lower surface nozzle 12 toward the central area of the lower surface of the substrate W in the rotating state (a lower removal liquid supply step, a lower removal liquid discharge step). The removal liquid supplied to the lower surface of the substrate W is diffused to the entire lower surface of the substrate W by centrifugal force.

By supplying the removal liquid to the upper surface of the substrate W, the treatment film 100 is peeled from the upper surface of the substrate W together with the object to be removed by the peeling action of the removal liquid (peeling step). The processing film 100 splits when peeled from the upper surface of the substrate W and becomes a film piece. Then, after the treatment film 100 is peeled off, the removal liquid is continued to be supplied to the upper surface of the substrate W, whereby the film pieces of the treatment film 100 after the split are removed from the substrate W together with the removal liquid. Thereby, the film piece of the processing film 100 in the state of removing the object is removed from the upper surface of the substrate W (removal step).

Here, the processing liquid supplied to the upper surface of the substrate W in the processing liquid supply step (step S2) shown in FIG. 5A sometimes wraps around the periphery of the substrate W to the lower surface of the substrate W. In addition, the processing liquid splashed from the substrate W sometimes splashes back from the shield 71 and adheres to the lower surface of the substrate W. Even in this case, as shown in FIG. 5D, the heat medium is supplied to the lower surface of the substrate W in the process film forming step. Therefore, the processing liquid can be removed from the lower surface of the substrate W by the flow of the heat medium.

Furthermore, the processing liquid adhering to the lower surface of the substrate W in the processing liquid supply step (step S2) may solidify or harden to form a solid. Even in this case, as shown in FIG. 5E, while the removal liquid is supplied to the upper surface of the substrate W in the removal step (step S5), the lower surface nozzle 12 is supplied (ejected) to the lower surface of the substrate W. Remove liquid. Thereby, the solid body can be peeled off and removed from the lower surface of the substrate W.

After the removal step (step S5), a flushing step (step S6) is performed. Specifically, the upper liquid removal valve 51 and the lower liquid removal valve 87 are closed. Thereby, the supply of the removal liquid to the upper surface and the lower surface of the substrate W is stopped. Then, the second nozzle moving unit 37 moves the second moving nozzle 10 to the home position. Then, as shown in FIG. 5F, the facing member elevating unit 61 moves the facing member 6 to the processing position. In the washing step, the substrate W is rotated at a specific washing speed, for example, 800 rpm. The processing position is a position farther upward and away from the upper surface of the substrate W than the approach position.

Then, with the opposing member 6 in the processing position, the upper flushing liquid valve 52 is opened. Thereby, the rinse liquid is supplied (discharged) from the central nozzle 11 toward the central area of the upper surface of the substrate W in the rotating state (upper rinse liquid supply step, upper rinse liquid spray step). The rinse liquid supplied to the upper surface of the substrate W is diffused to the entire upper surface of the substrate W by centrifugal force. Thereby, the removal liquid adhering to the upper surface of the substrate W is washed away by the rinse liquid.

Also, simultaneously with opening the upper flushing liquid valve 52, the lower flushing liquid valve 86 is opened. Thereby, the rinse liquid is supplied (discharged) from the lower surface nozzle 12 toward the central area of the lower surface of the substrate W in the rotating state (a lower rinse liquid supply step, a lower rinse liquid spray step). Thereby, the removing liquid adhering to the lower surface of the substrate W is washed away by the rinsing liquid. The rinse liquid is supplied to the upper surface and the lower surface of the substrate W for a specific time, for example, 35 seconds.

Then, the process film residue removal step (step S7) is performed. Specifically, the upper flushing liquid valve 52 and the lower flushing liquid valve 86 are closed. Thereby, the supply of the rinse liquid to the upper surface and the lower surface of the substrate W is stopped.

Then, with the opposing member 6 in the processing position, the processing film residue removal liquid valve 53 is opened. Thereby, as shown in FIG. 5G, the treatment film residue removal liquid is supplied (sprayed) from the central nozzle 11 toward the central area of the upper surface of the substrate W in a rotating state (treatment film residue removal solution supply step, treatment film residue removal solution spray step) ). The treatment film residue removal liquid is supplied to the upper surface of the substrate W for a specific time, for example, 30 seconds. In the process film residue removal step, the substrate W is rotated at a specific residue removal speed, for example, 300 rpm.

The treatment film residue removal liquid supplied to the upper surface of the substrate W is subjected to centrifugal force to diffuse radially, and spread to the entire upper surface of the substrate W. Thereby, the rinsing liquid on the upper surface of the substrate W is replaced by the processing film residue removal liquid. The treatment film residue removal liquid supplied to the upper surface of the substrate W dissolves the residue of the treatment film 100 remaining on the upper surface of the substrate W (treatment film residue), and then is discharged from the periphery of the upper surface of the substrate W (treatment film residue removal step ).

Then, a spin drying step is performed (step S8). Specifically, the treatment membrane residue removal liquid valve 53 is closed. Thereby, the supply of the treatment film residue removal liquid to the upper surface of the substrate W is stopped. Then, as shown in FIG. 5H, the facing member lifting unit 61 moves the facing member 6 to a drying position lower than the processing position. When the opposing member 6 is at the drying position, the distance between the opposing surface 6a of the opposing member 6 and the upper surface of the substrate W is, for example, 1.5 mm. Then, the gas valve 54 is opened. Thereby, gas is supplied to the space between the upper surface of the substrate W and the facing surface 6a of the facing member 6.

Then, the rotation motor 23 accelerates the rotation of the substrate W to rotate the substrate W at a high speed. The substrate W in the spin drying step is rotated at a drying speed, for example, 1500 rpm. The spin drying step is performed for a specific time, for example, during 30 seconds. Thereby, a relatively large centrifugal force acts on the processing film residue removal liquid on the substrate W, and the processing film residue removal liquid on the substrate W is thrown off to the periphery of the substrate W. In the spin drying step, the evaporation of the treatment film residue removal liquid is promoted by supplying gas to the space between the upper surface of the substrate W and the facing surface 6 a of the facing member 6.

Then, the rotation motor 23 stops the rotation of the substrate W. The shield raising and lowering unit 74 moves the first shield 71A and the second shield 71B to the lower position. The gas valve 54 is closed. Then, the facing member elevating unit 61 moves the facing member 6 to the upper position.

The transport robot CR enters the processing unit 2 and picks up the processed substrate W from the chuck pin 20 of the rotating chuck 5, and transports it out of the processing unit 2 (step S9). The substrate W is transferred from the transfer robot CR to the transfer robot IR, and is stored in the carrier C by the transfer robot IR.

In the spin drying step of the substrate processing, the upper surface of the substrate W is not dried by shaking off the DIW and other rinsing liquid on the substrate W, but the rinsing liquid on the substrate W is treated with a film residue removal liquid such as IPA. After the replacement, the processing liquid residue removal liquid on the substrate W is shaken off, thereby drying the upper surface of the substrate W. That is, the spin drying step is performed after replacing the surface tension with IPA having a lower surface tension than DIW. Therefore, the surface tension of the uneven pattern 160 (see FIG. 6) acting on the upper surface of the substrate W when the upper surface of the substrate W is dried can be reduced.

＜Construction of concave-convex pattern of substrate＞ As shown in FIG. 6, a fine concavo-convex pattern 160 is formed on the upper surface of the substrate W to be subjected to substrate processing. The concavo-convex pattern 160 includes fine convex structures 161 formed on the upper surface of the substrate W, and concave portions (grooves) 162 formed between adjacent structures 161.

The surface of the concavo-convex pattern 160, that is, the surfaces of the structure 161 (convex part) and the concave part 162 form a pattern surface 165 having concavities and convexities. The pattern surface 165 is included on the upper surface of the substrate W. The surface 161a of the structure 161 includes a front end surface 161b (top) and a side surface 161c, and the surface of the recess 162 includes a bottom surface 162a (bottom). When the structure 161 is cylindrical, a recess is formed on the inner side.

The surface layer 166 of the substrate W is the part of the substrate W that is at most about 1 nm away from the pattern surface 165 in the normal direction N of the pattern surface 165. The portion that is at most about 1 nm away from the pattern surface 165 in the normal direction N of the pattern surface 165 includes the portion that is at most about 1 nm away from the front end surface 161b of the structure 161 in the thickness direction T of the substrate W, and the bottom surface of the recess 162 The part separated by at most about 1 nm in the thickness direction T, and the part at most about 1 nm apart from the side surface 161c of the structure 161 in the orthogonal direction D with respect to the thickness direction T.

The structure 161 may include an insulator film or a conductor film. In addition, the structure 161 may be a laminated film obtained by laminating a plurality of films.

The concavo-convex pattern 160 is a fine pattern with an aspect ratio of 3 or more. The aspect ratio of the concavo-convex pattern 160 is 10-50, for example. The width L1 of the structure 161 may be about 5 nm to 45 nm, and the interval L2 between the structures 161 may be about 5 nm to several μm. The height (pattern height T1) of the structure 161 may be about 50 nm to 5 μm, for example. The pattern height T1 is the distance between the front end surface 161b of the structure 161 and the bottom surface 162a (bottom) of the recess 162.

＜Details of removal of treatment film＞ 7A to 8F are schematic diagrams for explaining the condition of the upper surface of the substrate in the above-mentioned substrate processing.

The condition of the upper surface of the substrate W when the removal target is removed from the substrate W differs according to the type of the removal target existing on the upper surface of the substrate W. The type of the removal target existing on the upper surface of the substrate W differs according to the type of processing performed on the upper surface of the substrate W before the substrate processing of the present embodiment is performed.

Specifically, when dry etching is performed before the substrate processing of the present embodiment, as shown in FIG. 7A, a film-like residue 103 (removal target film) covering at least a part of the surface of the substrate W is generated on the surface of the substrate W . That is, in this case, the film-like residue 103 is the object to be removed. On the other hand, when the CMP has been performed before the substrate processing in this embodiment, as shown in FIG. 8A, a spherical residue 113 is generated on the surface of the substrate W. That is, in this case, the spherical residue 113 is the object to be removed.

These removal objects are chemically bonded to the upper surface of the substrate W. "Chemical bonding between the object to be removed and the upper surface of the substrate W" means that the molecules or atoms constituting the object to be removed and the molecules or atoms constituting the surface layer 166 of the substrate W are bonded by covalent bonds, ionic bonds, metal bonds, or the like.

First, using FIGS. 7A to 7E, the condition of the upper surface of the substrate when the substrate processing of this embodiment is performed after dry etching is described.

As shown in FIG. 7A, before the process liquid supply step starts, the pattern surface 165 of the substrate W is covered by the film-like residue 103. The film-like residue 103 is formed of, for example, a carbon-based film or fluororesin containing fluorine atoms represented _{by CF X (X is a natural number greater than 1).} The fluorine atoms in the carbon-based film are due to the gas used in dry etching. The film-like residue 103 is not a film having a uniform thickness, but striped grooves 104 are formed, or the thickness of the film-like residue 103 is locally thinned with a recess 105.

The film-like residue 103 and the surface layer 166 of the substrate W are of different materials. Therefore, as the dissolving component contained in the treatment liquid, one that does not dissolve the surface layer 166 of the substrate W but dissolves the film-like residue 103 can be selected. Here, an example in which the dissolving component contained in the treatment liquid is one that dissolves the film-like residue 103 without dissolving the surface layer 166 of the substrate W will be described. That is, the film-like residue 103 (removal object) is a dissolution object.

When the treatment liquid comes into contact with the film-like residue 103, the film-like residue 103 starts to be dissolved by the dissolved components in the treatment solution. Cracks occur in the portion where the groove 104 or the recess 105 is formed in the film-like residue 103. The treatment liquid reaches the pattern surface 165 of the substrate W through the cracks. Taking the cracks generated in the film-like residue 103 as a starting point, the film-like residue 103 is split, as shown in FIG. 7B, to form a film of the film-like residue 103 (residue film 106). By the processing liquid that has reached the pattern surface 165, the residue film 106 is dissolved in the vicinity of the contact interface between the residue film 106 and the pattern surface 165 of the substrate W. Thereby, a gap G1 is formed between the pattern surface 165 of the substrate W and the residue film 106, and the processing liquid enters the gap G1.

In FIG. 7B, it is shown that a gap G1 is formed between all the residue film 106 and the pattern surface 165. However, it is not necessary to form a gap G1 between all the residue film 106 and the pattern surface 165. It is also possible to form a gap G1 between a part of the residue film 106 and the pattern surface 165.

In addition, even when the gap G1 is formed between the residue film 106 and the pattern surface 165, the residue film 106 does not need to completely float from the pattern surface 165. That is, there are cases where even when a gap G1 is formed between the residue film 106 and the pattern surface 165, the residue film 106 and the pattern surface 165 are in contact.

As shown in FIG. 7C, in the process film forming step, the process liquid is solidified or hardened by the evaporation of the solvent, and the process film 100 is formed. The processing film 100 is formed in a state where the processing liquid has entered between the upper surface of the substrate W and the residue film 106. Therefore, the formed treatment film 100 surrounds the residue film 106 and is firmly held.

The treatment film 100 includes a high solubility solid 110 (a high solubility component in a solid state), a low solubility solid 111 (a low solubility component in a solid state), and a dissolved component solid 112 (a dissolved component in a solid state). The treatment film 100 is divided into a part where the highly soluble solid 110 is concentrated and the part where the low soluble solid 111 is concentrated and present. The dissolved component solid 112 is uniformly formed in the entire processing film 100.

Furthermore, the treatment film 100 does not need to be a liquid-free solid, as long as it is cured to the extent that it can maintain a fixed shape. That is, the treatment film may contain each component in a liquid state (a high solubility component, a low solubility component, and a dissolved component), and may also contain each component in a state of being dissolved in a solvent.

Compared with the dissolved components in the treatment liquid, the dissolved components in the treatment film 100 are not easy to dissolve the film-like residue 103. Therefore, by the curing or hardening of the treatment liquid, the dissolution of the film-like residue 103 by the dissolving component is suppressed (dissolution suppression step).

As shown in FIG. 7D, in the removing step, the treatment film 100 is partially dissolved. If the removal liquid is supplied to the upper surface of the substrate W, the highly soluble solid 110 formed by the highly soluble component that is easier to dissolve in the removal liquid than the low soluble component is mainly dissolved. That is, the highly soluble solid 110 is selectively dissolved.

"Selectively dissolving the highly soluble solid 110" does not mean only dissolving the highly soluble solid 110. The meaning of "selectively dissolving the highly soluble solid 110" means that the low soluble solid 111 is also slightly dissolved, but most of the highly soluble solid 110 is dissolved.

Specifically, the through-hole 107 is formed in the portion where the highly soluble solid 110 is concentrated in the processing film 100 (through-hole forming step). The through hole 107 is particularly easy to be formed in the portion where the highly soluble solid 110 extends in the normal direction N of the pattern surface 165. The through hole 107 has a size of, for example, several nanometers in diameter in a plan view.

It may be that the low solubility solid 111 is also dissolved in the removal liquid. However, since the solubility of the low-solubility component in the removal liquid is lower than that of the high-solubility component, the low-solubility solid 111 is only slightly dissolved by the removal liquid in the vicinity of its surface. Therefore, the removal liquid reaching the vicinity of the upper surface of the substrate W through the through hole 107 slightly dissolves the portion of the low-solubility solid 111 near the upper surface of the substrate W. Thereby, as shown in the enlarged view of FIG. 7D, the removing liquid gradually dissolves the low-solubility solid 111 near the upper surface of the substrate W, while entering the gap G2 between the processing film 100 and the upper surface of the substrate W (removing liquid Go to step).

And, for example, the treatment film 100 splits from the periphery of the through hole 107 as a starting point to become a film. As shown in FIG. Peeling (treatment film splitting step, peeling step). Then, the residue film 106 (removal object) is pushed out of the substrate W together with the process film 100 in the state held by the process film 100, and removed from the upper surface of the substrate W (removal step).

Furthermore, there may be cases where the removal liquid hardly dissolves the low-solubility solid 111. In this case, the processing film 100 is peeled from the substrate W by entering the tiny gap G2 between the processing film 100 and the upper surface of the substrate W.

According to the configuration in which the substrate processing of the present embodiment is performed after dry etching, the film-like residue 103 (removal object) is partially dissolved by the dissolved components contained in the processing liquid. Therefore, by performing the processing liquid supply step, the processing liquid easily enters between the film-like residue 103 and the upper surface of the substrate W. In the process film forming step, if the process liquid is solidified or hardened in a state where the process liquid has entered between the film-like residue 103 and the upper surface of the substrate W, a part of the process film 100 is formed on the film-like residue 103 and the substrate W. Between the surface. Therefore, in the removal step, the treatment film 100 holds the residue film 106 (removal object) with a sufficient holding force while being removed from the upper surface of the substrate W by the removal liquid. As a result, the film-like residue 103 (removal object) can be removed from the upper surface of the substrate W efficiently.

However, different from the substrate processing of this embodiment, after supplying a solution containing dissolved components (for example, hydrofluoric acid) to the upper surface of the substrate W, the solution is washed away with a rinse solution, and thereafter, there will be no solution. In the method of supplying the processing liquid of the components to the substrate to form the processing film, a plurality of liquids are sequentially supplied to the upper surface of the substrate W. Therefore, every time the liquid on the substrate W is replaced, a turbulent flow is likely to be generated around the film-like residue 103 (removal object). Furthermore, when the hydrofluoric acid is replaced with a rinse liquid, the liquid around the film-like residue 103 changes from acidity to neutrality. There is a possibility that the film-like residue 103 once separated from the upper surface of the substrate W by the dissolving liquid due to the generation of turbulence or the change of the liquid properties may adhere to the upper surface of the substrate W again before being held in the processing film 100.

On the other hand, in the substrate processing method of this embodiment, after the processing liquid containing the dissolved component is supplied to the upper surface of the substrate W, the processing film 100 is formed without replacing the processing liquid with another liquid. Therefore, the treatment film 100 can be formed quickly after the film-like residue 103 is partially dissolved. Therefore, the treatment film 100 can be formed while maintaining the state where the residue film 106 (removal object) has been separated from the upper surface of the substrate W.

Furthermore, the step of supplying the dissolving liquid to the upper surface of the substrate W and the step of supplying the rinse liquid to the upper surface of the substrate W can be omitted. Therefore, the time required for substrate processing can be shortened.

In addition, in this substrate processing, the dissolution of the film-like residue 103 by the dissolving component is suppressed by solidifying or hardening the processing liquid (dissolution suppressing step). Therefore, excessive dissolution of the film-like residue 103 based on the dissolved components can be avoided.

In addition, in the substrate processing, the solute in the processing liquid has a soluble component, a high soluble component, and a low soluble component that is less soluble in the removal liquid than the high soluble component. The treatment film 100 has a high solubility solid 110, a low solubility solid 111, and a dissolved component solid 112. In the removal step, the highly soluble solid 110 in the treatment film 100 is selectively dissolved in the removal liquid.

Therefore, by dissolving the highly soluble solid 110 in the removal liquid, the removal liquid can act on the contact interface between the processing film 100 and the substrate W. On the other hand, the low-solubility components in the treatment film 100 do not dissolve but are maintained in a solid state. Therefore, it is possible to make the removal liquid act on the contact interface between the low solubility solid 111 and the substrate W while holding the object to be removed by the low solubility solid 111. As a result, the processing film 100 can be quickly removed from the upper surface of the substrate W, and the film-like residue 103 (removal target) together with the processing film 100 can be efficiently removed from the upper surface of the substrate W.

In this substrate processing, the film-like residue 103 (removal object) is chemically bonded to the upper surface of the substrate W. In order to separate the film-like residue 103 (removal object) retained on the processing film 100 from the upper surface of the substrate W, it is considered that the self-removing liquid acts on the film by supplying a large flow of a removing liquid to the upper surface of the substrate W. A method to increase the physical force (kinetic energy) of the shaped residue 103. However, when the film-like residue 103 is chemically bonded to the upper surface of the substrate W, even if the film-like residue 103 is held by the processing film 100 and the physical force received by the self-removing liquid increases, only the physical force of the removal liquid It is also difficult to separate the film-like residue 103 from the upper surface of the substrate W.

Therefore, if the film-like residue 103 is partially dissolved by the dissolved components contained in the treatment liquid as in the substrate processing, the film-like residue 103 (residue film The sheet 106) is separated from the upper surface of the substrate W. Therefore, even when the film-like residue 103 is chemically bonded to the upper surface of the substrate W, the film-like residue 103 can be efficiently removed from the upper surface of the substrate W.

In addition, in this substrate processing, the film-like residue 103 covers at least a part of the upper surface of the substrate. Unlike this substrate processing, when the processing film 100 is formed from a processing liquid that does not have a dissolved component, the processing liquid is difficult to enter between the film-like residue 103 and the pattern surface 165 of the substrate W.

However, in this substrate processing, the film-like residue 103 is partially dissolved by the dissolved components in the processing liquid. Thereby, a gap G1 between the film-like residue 103 and the pattern surface 165 of the substrate W is formed. Therefore, the processing liquid can enter between the film-like residue 103 and the pattern surface 165 of the substrate W.

Furthermore, the film-like residue 103 is split by the dissolved components in the treatment liquid. Therefore, the processing liquid can more efficiently enter between the residue film 106 and the pattern surface 165 of the substrate W through the gap between the split films.

Next, using FIGS. 8A to 8F, the condition of the upper surface of the substrate W when the substrate processing of this embodiment has been performed after CMP is described.

As shown in FIG. 8A, before the process liquid supply step is started, a spherical residue 113, for example, adheres to the pattern surface 165 of the substrate W. The residue 113 is not limited to a spherical shape, and may have other shapes such as an ellipsoid shape.

The spherical residue 113 is, for example, an abrasive used in CMP. Even if the material of the spherical residue 113 is different from the material of the surface layer 166 of the substrate W, the surface layer 166 of the substrate W is dissolved by the dissolved components to the same extent as the spherical residue 113. The material of the spherical residue 113 may be the same as that of the surface layer 166 of the substrate W. Therefore, when the substrate processing is performed after CMP, the surface layer 166 of the substrate W and the spherical residue 113 (removal object) are the objects to be dissolved.

As shown in FIG. 8B, if the processing liquid contacts the pattern surface 165 of the substrate W, the surface layer 166 of the substrate W is partially dissolved by the dissolved components in the processing liquid. The part near the surface of the spherical residue 113 is also partially dissolved by contact with the treatment liquid. Therefore, a gap G3 is formed between the pattern surface 165 of the substrate W and the spherical residue 113, and the processing liquid enters the gap G3.

As shown in FIG. 8C, in the process film forming step, the process liquid is solidified or hardened by the evaporation of the solvent to form the process film 100. The processing film 100 is formed in a state where the processing liquid has entered the gap G3 between the pattern surface 165 of the substrate W and the spherical residue 113. Therefore, the formed treatment film 100 surrounds the spherical residue 113 and is firmly held.

The treatment film 100 includes a highly soluble solid 110 (a highly soluble component in a solid state), a low soluble solid 111 (a low soluble component in a solid state), and a dissolved component solid 112 (a soluble component in a solid state). The treatment film 100 is divided into a part where the highly soluble solid 110 is concentrated and the part where the low soluble solid 111 is concentrated and present. The dissolved component solid 112 is uniformly formed in the entire processing film 100.

Furthermore, the treatment film 100 does not need to be a liquid-free solid, as long as it is cured to the extent that it can maintain a fixed shape. That is, the treatment film may contain each component in a liquid state (a high solubility component, a low solubility component, and a dissolved component), and may also contain each component in a state of being dissolved in a solvent.

Compared with the dissolved components in the processing liquid, the dissolved components in the processing film 100 are not easy to dissolve the spherical residue 113 and the surface layer 166 of the substrate W. Therefore, the dissolution of the spherical residue 113 and the surface layer 166 of the substrate W by the dissolving component due to the solidification or hardening of the treatment liquid is suppressed (dissolution suppression step).

After the processing film 100 is formed, the processing film 100 and the pattern surface 165 are also in contact. The solvent slightly remains in the treatment film 100. Therefore, in the processing film 100, there are also dissolved components that have been dissolved in the solvent. Therefore, as shown in FIG. 8D, the surface layer 166 of the substrate W is dissolved by the dissolving component in the processing film 100 near the contact interface between the processing film 100 and the substrate W. Therefore, the dissolved components in the processing film 100 near the contact interface between the processing film 100 and the substrate W are consumed.

The processing film 100 is formed by curing or hardening the processing liquid, and therefore, the dissolved components in the processing film 100 are not easily diffused. Therefore, with the consumption of the dissolved components in the processing film 100 near the contact interface between the processing film 100 and the pattern surface 165 of the substrate W, the dissolution of the surface layer 166 of the substrate W based on the dissolved components in the processing film 100 is suppressed.

Since the dissolution of the surface layer 166 of the substrate W based on the dissolved components in the processing film 100 is suppressed, a gap G4 is formed between the processing film 100 and the pattern surface 165 of the substrate W. Thereby, the contact area between the processing film 100 and the pattern surface 165 is reduced, and therefore, the dissolution of the surface layer 166 of the substrate W by the dissolving component is suppressed.

As shown in FIG. 8E, in the removing step, the treatment film 100 is partially dissolved. If the removal liquid is supplied to the pattern surface 165 of the substrate W, the highly soluble solid 110 formed by the highly soluble component that is easier to dissolve in the removal liquid than the low soluble component is mainly dissolved. That is, the highly soluble solid 110 is selectively dissolved.

Specifically, the through-hole 107 is formed in the portion where the highly soluble solid 110 is concentrated in the processing film 100 (through-hole forming step). The through hole 107 is particularly easy to be formed in the portion where the highly soluble solid 110 extends in the normal direction N of the pattern surface 165. The through hole 107 has a size of, for example, several nanometers in diameter in a plan view.

It may be that the low solubility solid 111 is also dissolved in the removal liquid. However, compared with the high solubility solid 110, the low solubility solid 111 is not easily dissolved by the removal liquid. Only the vicinity of the pattern surface 165 of the low-solubility solid 111 is slightly dissolved by the removal liquid. Therefore, the removal liquid reaching the vicinity of the pattern surface 165 of the substrate W through the through hole 107 slightly dissolves the portion of the low solubility solid 111 near the pattern surface 165 of the substrate W. Thereby, the removing liquid gradually dissolves the low-soluble solids 111 near the pattern surface 165 of the substrate W, and enters the gap G4 between the processing film 100 and the pattern surface 165 of the substrate W (the removing liquid entering step).

And, for example, the processing film 100 splits from the periphery of the through hole 107 as a starting point to become a diaphragm. As shown in FIG. W peeling (treatment film splitting step, peeling step). Then, the spherical residue 113 is pushed out of the substrate W together with the processing film 100 in a state held by the processing film 100 and removed from the pattern surface 165 of the substrate W (removal step).

According to the configuration in which the substrate processing of the present embodiment is performed after CMP, the spherical residue 113 (removal object) is partially dissolved by the dissolving component contained in the processing liquid. Therefore, by performing the processing liquid supply step, the processing liquid easily enters between the spherical residue 113 and the pattern surface 165 of the substrate W. In the process film forming step, if the process liquid is solidified or hardened in a state where the process liquid has entered between the spherical residue 113 and the pattern surface 165 of the substrate W, a part of the process film 100 is formed on the spherical residue 113 Between and the surface of the substrate W. Therefore, in the removal step, the process film 100 retains the spherical residue 113 (removal object) with sufficient holding force, and is removed from the pattern surface 165 of the substrate W by the removal liquid. As a result, the spherical residue 113 (removal object) can be removed from the pattern surface 165 of the substrate W efficiently.

However, unlike the substrate processing of this embodiment, after supplying a solution containing dissolved components (for example, hydrofluoric acid) to the pattern surface 165 of the substrate W, the solution is washed away with a rinse solution, and thereafter, no In the method of supplying a processing liquid of dissolved components to a substrate to form a processing film, a plurality of liquids are sequentially supplied to the pattern surface 165 of the substrate W. Therefore, every time the liquid on the substrate W is replaced, a turbulent flow is likely to be generated around the spherical residue 113 (removal object). Furthermore, when the hydrofluoric acid is replaced with the flushing liquid, the liquid around the film-like residue 103 changes from acidic to neutral. There is a possibility that the spherical residue 113 separated once from the pattern surface 165 of the substrate W by the turbulent flow or the change of the liquid properties may be attached to the pattern surface 165 of the substrate W again before being held in the processing film 100 .

On the other hand, in the substrate processing method of this embodiment, after the processing liquid containing the dissolved component is supplied to the pattern surface 165 of the substrate W, the processing film 100 is formed without replacing the processing liquid with another liquid. Therefore, the treatment film 100 can be formed quickly after the dissolution target is dissolved. Therefore, the treatment film 100 can be formed while maintaining the spherical residue 113 (removal object) separated from the pattern surface 165 of the substrate W.

Furthermore, the step of supplying the dissolving liquid to the upper surface of the substrate W and the step of supplying the rinse liquid to the upper surface of the substrate W can be omitted. Therefore, the time required for substrate processing can be shortened.

In addition, in the substrate processing, the dissolution of the spherical residue 113 with the dissolved component is suppressed by solidifying or hardening the processing liquid (dissolution suppressing step). Therefore, excessive dissolution of the spherical residue 113 based on the dissolved components can be avoided.

In addition, in the substrate processing, the solute in the processing liquid has soluble components, highly soluble components, and low soluble components that are less soluble in the removal liquid than the highly soluble components. The treatment film 100 has a high solubility solid 110, a low solubility solid 111, and a dissolved component solid 112. In the removal step, the highly soluble solid 110 in the treatment film 100 is selectively dissolved in the removal liquid. Therefore, by dissolving the highly soluble solid 110 in the removal liquid, the removal liquid can act on the contact interface between the processing film 100 and the substrate W. On the other hand, the low-solubility components in the treatment film 100 do not dissolve but are maintained in a solid state. Therefore, it is possible to make the removal liquid act on the contact interface between the low-soluble solid 111 and the substrate W while holding the object to be removed by the low-soluble solid 111. As a result, the processing film 100 can be quickly removed from the pattern surface 165 of the substrate W, and the spherical residue 113 (removal object) together with the processing film 100 can be efficiently removed from the pattern surface 165 of the substrate W.

In this substrate processing, the spherical residue 113 (removal object) and the pattern surface 165 of the substrate W are chemically bonded. In order to separate the spherical residue 113 (removal object) held in the process film 100 from the pattern surface 165 of the substrate W, it is considered that the self-removing liquid can be made by supplying a large flow of removing liquid to the pattern surface 165 of the substrate W. A method to increase the physical force (kinetic energy) acting on the spherical residue 113.

However, when the spherical residue 113 is chemically bonded to the pattern surface 165 of the substrate W, even if the spherical residue 113 is held by the processing film 100 and the physical force of the self-removing liquid increases, only the removal of the liquid The physical force is also difficult to separate the spherical residue 113 from the pattern surface 165 of the substrate W.

Therefore, if both the surface layer 166 of the substrate W and the spherical residue 113 are partially dissolved by the dissolved components contained in the processing liquid as in the substrate processing, the spherical residue 113 and the pattern surface 165 of the substrate W can be ignored. This bond strength separates the spherical residue 113 from the pattern surface 165 of the substrate W. Therefore, even when the spherical residue 113 is chemically bonded to the pattern surface 165 of the substrate W, the spherical residue 113 can be efficiently removed from the pattern surface 165 of the substrate W.

In addition, in the substrate processing, the spherical residue 113 covers at least a part of the pattern surface 165 of the substrate. Different from this substrate processing, when the processing film 100 is formed from a processing liquid that does not have a dissolved component, the processing liquid is difficult to enter between the spherical residue 113 and the pattern surface 165 of the substrate W.

However, in the substrate processing, both the spherical residue 113 and the pattern surface 165 of the substrate W are partially dissolved by the dissolved components in the processing liquid. Thereby, a gap G3 is formed between the spherical residue 113 and the pattern surface 165 of the substrate W. Therefore, the treatment liquid can enter between the spherical residue 113 and the pattern surface 165 of the substrate W.

In addition, in the substrate processing, not only when the processing liquid is present on the pattern surface 165 of the substrate W, after the processing film 100 is formed, the surface layer 166 of the substrate W is also dissolved by the dissolving components in the processing film 100. Therefore, the adhesion between the processing film 100 and the pattern surface 165 of the substrate W can be reduced. Thereby, in the removing step after the processing film forming step, the processing film 100 is easily peeled off from the pattern surface 165 of the substrate W. That is, the processing film 100 in the state where the removal target object (spherical residue 113) is maintained can be removed from the pattern surface 165 of the substrate W with high efficiency.

The processing film 100 is formed by curing or hardening the processing liquid, and therefore, has lower fluidity than the liquid film 101 of the processing liquid. Therefore, the gap G4 formed between the processing film 100 and the pattern surface 165 of the substrate W is not buried by the processing film 100 but is maintained. Therefore, in the removal step after the processing film formation step, the removal liquid easily enters the gap G4 between the processing film 100 and the pattern surface 165 of the substrate W. Thereby, the processing film 100 in the state where the object to be removed (spherical residue 113) is maintained can be removed from the pattern surface 165 of the substrate W efficiently.

＜Details of treatment solution＞ Hereinafter, each component in the treatment liquid used in the above-mentioned embodiment will be described.

In the following, descriptions such as "Cx～y", "Cx～Cy" and "Cx" refer to the number of carbons in the molecule or substituent. For example, C _{1 -6} alkyl refers to an alkyl chain (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.) having _{1 to 6 carbons.}

When the polymer has multiple types of repeating units, the repeating units are copolymerized. As long as it is not particularly limited and mentioned, the copolymerization may be any of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof. When a polymer or resin is represented by a structural formula, n or m in parentheses indicates the number of repetitions.

＜Low solubility component＞ (A) Low solubility components include novolac, polyhydroxystyrene, polystyrene, polyacrylic acid derivatives, polymaleic acid derivatives, polycarbonate, polyvinyl alcohol derivatives, polymethacrylic acid derivatives , And at least one of the copolymers of combinations thereof. Preferably, (A) the low solubility component may also include at least one copolymer of novolac, polyhydroxystyrene, polyacrylic acid derivative, polycarbonate, polymethacrylic acid derivative, and combinations thereof. Furthermore, it is preferable that (A) a low-solubility component may also contain at least one of a copolymer of novolac, polyhydroxystyrene, polycarbonate, and combinations thereof. The novolak may also be a phenol novolak.

The treatment liquid may also contain one or two or more of the above-mentioned preferred examples in combination as (A) the low-solubility component. For example, (A) the low solubility component may also contain both novolak and polyhydroxystyrene.

A preferred aspect is that (A) the low-solubility component is formed into a film by drying, and the film is not mostly dissolved by the removal liquid, but peels off while maintaining the removal target. Furthermore, it is allowed to use the removal liquid to dissolve a very small part of the low solubility component (A).

It is preferable that (A) the low solubility component does not contain fluorine and/or silicon, and it is more preferable that it does not contain both.

The aforementioned copolymerization is preferably random copolymerization or block copolymerization.

It is not intended to limit the scope of patent applications, but as specific examples of (A) low-solubility components, each compound represented by the following chemical formula 1 to chemical formula 7 can be cited.

[化1] [化1]

[化2] [化2]

(星號＊表示向鄰接之結構單元之鍵結。)[化3] [化3]

(The asterisk * indicates the bonding to adjacent structural units.)

(R指C_{1 ～ 4} 烷基等取代基。星號＊表示向鄰接之結構單元之鍵結。)[化4] [化4]

(R means C _{1 ~ 4} alkyl group substituents. The asterisk * indicates the bond to the adjacent structural units.)

[化5] [化5]

[化6] [化6]

(Me指甲基。)[化7] [化7]

(Me refers to methyl.)

(A) The weight average molecular weight (Mw) of the low solubility component is preferably 150 to 500,000, more preferably 300 to 300,000, still more preferably 500 to 100,000, and still more preferably 1,000 to 50,000.

(A) Low-solubility components can be obtained by synthesis. It can also be purchased. In the case of purchase, as an example, the following suppliers can be cited. The supplier can also synthesize (A) polymer. Novolac: Showa Chemicals Co., Ltd., Asahi Organic Materials Co., Ltd., Kunei Chemical Industry Co., Ltd., Sumitomo Bakelite Co., Ltd. Polyhydroxystyrene: Japan Soda (shares), Maruzen Petrochemical (shares), Toho Chemical Industry (shares) Polyacrylic acid derivatives: (Stock) Nippon Shokubai Polycarbonate: Sigma-Aldrich Polymethacrylic acid derivatives: Sigma-Aldrich

Compared with the total mass of the treatment liquid, the (A) low solubility component is 0.1-50% by mass, preferably 0.5-30% by mass, more preferably 1-20% by mass, and still more preferably 1-10% by mass . That is, the total mass of the treatment liquid is set to 100% by mass, and the (A) low-solubility component is 0.1 to 50% by mass based on this. That is, "compared with ~" can be renamed "based on ~". As long as it is not specifically mentioned, the same applies to the following.

The solubility can be evaluated by a known method. For example, under the conditions of 20°C to 35°C (more preferably 25±2°C), add 100 ppm of the above (A) or the following (B) to 5.0% by mass ammonia water in a flask, and close the lid, It can be determined based on whether (A) or (B) has dissolved or not by using a shaker for 3 hours. Vibration can also be stirring. Dissolution can also be judged visually. If it is not dissolved, the solubility is set to less than 100 ppm, and if it is dissolved, the solubility is set to 100 ppm or more. When the solubility is less than 100 ppm, it is regarded as insoluble or poorly soluble, and when the solubility is more than 100 ppm, it is regarded as soluble. In a broad sense, soluble includes slightly soluble. The solubility is lower in the order of insoluble, insoluble, and soluble. In a narrow sense, the slightly soluble phase has lower solubility than soluble, and higher solubility than insoluble.

＜Highly soluble components＞ (B) Highly soluble component system (B') crack promoting component. (B') The crack-promoting component contains a hydrocarbon, and further contains a hydroxyl group (-OH) and/or a carbonyl group (-C(=O)-). When (B') the crack promoting component is a polymer, one of the structural units contains a hydrocarbon per unit, and further has a hydroxyl group and/or a carbonyl group. The carbonyl group includes carboxylic acid (-COOH), aldehyde, ketone, ester, amide, and enone, and carboxylic acid is preferred.

It is not intended to limit the scope of the patent application. Although not bound by theory, it is considered that the treatment film is formed on the substrate by drying the treatment liquid, and when the removal liquid peels off the treatment film, (B) highly soluble components are generated which cause the treatment film to peel off. The opportunity part. For this reason, (B) the high-solubility component is preferably one having higher solubility in the removal liquid than (A) the low-solubility component. As the aspect in which the crack promoting component (B') contains a ketone as a carbonyl group, cyclic hydrocarbons can be cited. As a specific example, 1,2-cyclohexanedione or 1,3-cyclohexanedione may be mentioned.

As a more specific aspect, the (B) highly soluble component is represented by at least any one of the following (B-1), (B-2), and (B-3).

(B-1) A compound containing 1 to 6 (preferably 1 to 4) of the following chemical formula 8 as a structural unit, and each structural unit is bonded with a linker L ₁ . Here, the linking group L ₁ may be a single bond, or may be a C _{1 to 6} alkylene group. The above-mentioned C1-6 alkylene group connects the structural unit as a linking group, and is not limited to a divalent group. Preferably it is 2 to 4 valence. The above-mentioned C _{1 to 6} alkylene group may be either straight chain or branched chain.

[化8] [化8]

Cy ₁ hydrocarbon ring of C _{5 ~ 30,} preferably a phenyl group, a naphthyl group, or cyclohexane, more preferably a phenyl group. As a preferred aspect, the connecting base L ₁ connects a plurality of Cy ₁ .

R1 are each independently C _{1 ~ 5} alkyl group, preferably methyl, ethyl, propyl or butyl. The above-mentioned C _{1 to 5} alkyl group may be either straight chain or branched chain.

n _b1 is 1, 2 or 3, preferably 1 or 2, more preferably 1. n _{b1 '} is 0, 1, 2, 3, or 4, preferably 0, 1, or 2.

The following chemical formula 9 is a chemical formula obtained by expressing the structural unit described in chemical formula 8 using the linking group L _9. The linking group L _{9 is} preferably a single bond, methylene, ethylene or propylene.

[化9] [化9]

It is not intended to limit the scope of patent applications, but as preferred examples of (B-1), 2,2-bis(4-hydroxyphenyl)propane, 2,2'-methylenebis(4-methyl) Phenol), 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, 1,3-cyclohexanediol, 4,4'-dihydroxybiphenyl, 2,6-Naphthalenediol, 2,5-di-tert-butylhydroquinone, 1,1,2,2-tetra(4-hydroxyphenyl)ethane. They can also be obtained by polymerization or condensation.

As an example, 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol represented by the following chemical formula 10 will be described. In (B-1), this compound has 3 structural units of Chemical Formula 8, and the structural units are bonded by a linking group L ₁ (methylene). n _b1 =n _{b1 '} =1, and R ₁ is a methyl group.

(B-2)由下述化學式11表示。[化10] [化10]

(B-2) is represented by the following chemical formula 11.

[化11] [化11]

R _21, R _22, R ₂₃ and R ₂₄ are each independently hydrogen or alkyl _{having 1 to 5} C, the preferred are hydrogen, methyl, ethyl, isopropyl or tert-butyl, more preferably hydrogen, Methyl or ethyl, more preferably methyl or ethyl.

Linking group linking group L ₂₁ and L ₂₂ are each independently C _{1 to 20} of the extension alkyl, C _{1 ~ 20} of the extension cycloalkyl, C _2-4 stretch of alkenyl, C _2-4 of extension or alkynyl group C _{6 ～ 20} aryl extension. These groups may also be substituted by C _{1 ～ 5} alkyl groups or hydroxy groups. Here, the so-called alkenylene group refers to a divalent hydrocarbon having one or more double bonds, and the so-called alkynylene group refers to a divalent hydrocarbon group having one or more triple bonds. The linking group L ₂₁ and the linking group L _{22 are} preferably C _{2 to 4} alkylene, ethynyl (C ₂ alkynylene) or phenylene, more preferably C _{2 to 4} alkylene or ethynyl , More preferably an ethynyl group.

n _b2 is 0, 1, or 2, preferably 0 or 1, more preferably 0.

It is not intended to limit the scope of patent applications, but as preferred examples of (B-2), 3,6-dimethyl-4-octyne-3,6-diol, 2,5-dimethyl- 3-hexyne-2,5-diol. As one of the other forms, 3-hexyne-2,5-diol, 1,4-butynediol, 2,4-hexadiyne-1,6-diol, 1,4-butanediol, Cis-1,4-dihydroxy-2-butene and 1,4-benzenedimethanol can also be cited as preferred examples of (B-2).

(B-3) A polymer containing a structural unit represented by the following chemical formula 12 and having a weight average molecular weight (Mw) of 500 to 10,000. Mw is preferably 600 to 5,000, more preferably 700 to 3,000.

此處，R₂₅ 係-H、-CH₃ 或-COOH，較佳為-H或-COOH。亦容許1個(B-3)聚合物包含分別由化學式12表示之2種以上之結構單元。[化12] [化12]

Here, R ₂₅ is -H, -CH ₃ or -COOH, preferably -H or -COOH. It is also allowed that one (B-3) polymer contains two or more structural units represented by Chemical Formula 12, respectively.

It is not intended to limit the scope of the patent application, but as a preferable example of the (B-3) polymer, a polymer of acrylic acid, maleic acid, or a combination thereof can be cited. Polyacrylic acid and maleic acid acrylic copolymer are further preferred examples.

In the case of copolymerization, random copolymerization or block copolymerization is preferred, and random copolymerization is more preferred.

As an example, the maleic acid acrylic copolymer represented by the following chemical formula 13 will be described. This copolymer is contained in (B-3), has two kinds of structural units represented by Chemical Formula 12, and R ₂₅ is -H in one structural unit. In another structural unit, R ₂₅ is -COOH.

[化13] [化13]

Needless to say, the treatment liquid may also contain one or more of the above-mentioned preferred examples in combination as the (B) highly soluble component. For example, (B) the highly soluble component may also include both 2,2-bis(4-hydroxyphenyl)propane and 3,6-dimethyl-4-octyne-3,6-diol.

(B) The molecular weight of the highly soluble component can be 80 to 10,000. The molecular weight of the highly soluble component is preferably from 90 to 5,000, more preferably from 100 to 3,000. When (B) the highly soluble component is a resin, a polymer, or a polymer, the molecular weight is represented by the weight average molecular weight (Mw).

(B) Highly soluble components can be obtained by synthesis or purchased. As suppliers, Sigma-Aldrich, Tokyo Chemical Industry, and Nippon Shokubai can be cited.

In the treatment liquid, the mass of the (B) high-solubility component and the (A) low-solubility component are preferably 1-100% by mass, more preferably 1-50% by mass. In the treatment liquid, the mass of the (B) highly soluble component is more preferably 1 to 30% by mass compared to the mass of the (A) low soluble component.

＜Solvent＞

(C) The solvent preferably contains an organic solvent. (C) The solvent may also be volatile. Volatile means higher volatility than water. For example, the boiling point of the solvent of (C) at 1 atmosphere is preferably 50 to 250°C. The boiling point of the solvent under 1 atmosphere is more preferably 50 to 200°C, and still more preferably 60 to 170°C. The boiling point of the solvent under 1 atmosphere is more preferably 70 to 150°C. (C) The solvent may also contain a small amount of pure water. (C) The pure water contained in the solvent is preferably 30% by mass or less compared to the whole (C) solvent. The pure water contained in the solvent is more preferably 20% by mass or less, and still more preferably 10% by mass or less. The pure water contained in the solvent is more preferably 5% by mass or less. It is also a preferred form that the solvent does not contain pure water (0% by mass). The pure water is preferably DIW.

Examples of organic solvents include alcohols such as isopropanol (IPA), ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, and ethylene glycol monomethyl ether. Ethylene glycol monoalkyl ether acetates such as alcohol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether (PGEE) and other propylene glycol monoalkyl ethers, propylene glycol monomethyl ether acetate (PGMEA) , Propylene glycol monoethyl ether acetate and other propylene glycol monoalkyl ether acetates, methyl lactate, ethyl lactate (EL) and other lactate esters, toluene, xylene and other aromatic hydrocarbons, methyl ethyl ketone, 2- Ketones such as heptanone and cyclohexanone, amides such as N,N-dimethylacetamide and N-methylpyrrolidone, lactones such as γ-butyrolactone, etc. These organic solvents can be used individually or in mixture of 2 or more types.

As a preferred aspect, (C) the organic solvent contained in the solvent is selected from any combination of IPA, PGME, PGEE, EL, PGMEA, and the like. When the organic solvent is a combination of two kinds, the volume ratio is preferably 20:80 to 80:20, more preferably 30:70 to 70:30.

Compared with the total mass of the treatment liquid, (C) the solvent is 0.1 to 99.9% by mass. Compared with the total mass of the treatment liquid, the (C) solvent is preferably 50 to 99.9% by mass, more preferably 75 to 99.5% by mass. Compared with the total mass of the treatment liquid, the (C) solvent is more preferably 80 to 99% by mass, and more preferably 85 to 99% by mass.

＜Other additives＞

The treatment liquid of the present invention may further include (D) other additives. As an aspect of the present invention, (D) other additives include surfactants, acids, alkalis, antibacterial agents, bactericides, preservatives, or antifungal agents (preferably surfactants), and they may also be included. Any combination of them.

As one aspect of the present invention, compared with the mass of (A) low solubility components in the treatment liquid, (D) other additives (the sum in the case of plural kinds) is 0-100 mass (preferably It is 0 to 10% by mass, more preferably 0 to 5% by mass, still more preferably 0 to 3% by mass, and still more preferably 0 to 1% by mass). It is also an aspect of the present invention that the treatment liquid does not contain (D) other additives (0% by mass).

＜Dissolved ingredients＞

(E) The dissolved component is, for example, an inorganic acid, an organic acid, or an organic base. As the inorganic acid used as the dissolving component, HF, HCl, H ₃ PO ₄ , H ₂ SO ₄ and the like can be mentioned. Examples of organic acids used as dissolving components include formic acid, acetic acid, butyric acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monofluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, monobromoacetic acid, tribromoacetic acid, Perfluoropropionic acid, perfluorobutyric acid, perfluorovaleric acid, perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, perfluorododecanoic acid, 3 , 3,3-Trifluoro-2-(trifluoromethyl)propionic acid, 3H-tetrafluoropropionic acid, 5H-octafluorovaleric acid, 7H-dodecafluoroheptanoic acid, methanesulfonic acid, etc.

The organic acid used as the dissolving component is not limited to the above, and may be a fluorinated carboxylic acid or sulfonic acid other than the above-mentioned carboxylic acid or sulfonic acid. The fluorinated carboxylic acid refers to a carboxylic acid in which part or all of the hydrogen atoms of the alkyl group (for example, methyl, ethyl, propyl, etc.) adjacent to the carboxyl group are replaced by fluorine atoms.

Similarly, fluorinated sulfonic acid refers to a sulfonic acid in which part or all of the hydrogen atoms of an alkyl group (for example, methyl, ethyl, propyl, etc.) adjacent to the sulfo group are replaced by fluorine atoms.

As the organic base used as the dissolving component, ammonia, hydroxylamine, primary amine, secondary amine, tertiary amine, quaternary ammonium salt, polyamine, and the like can be cited.

＜Anti-corrosion component＞

As the (F) anti-corrosion component, in addition to BTA, uric acid, caffeine, pterin, adenine, glyoxylic acid, glucose, fructose, mannose, etc. can also be cited.

<Other embodiments>

The present invention is not limited to the above-described embodiments, and can be implemented in other forms.

For example, in the above-mentioned embodiment, the case where the removal target (film-like residue 103) is partially dissolved by the dissolved component contained in the treatment liquid (refer to FIGS. 7A to 7E), and the dissolution caused by the dissolution contained in the treatment liquid The case where the component dissolves the removal target (spherical residue 113) and the surface layer 166 of the substrate W locally (refer to FIGS. 8A to 8F) has been described. However, unlike the above-mentioned embodiment, the dissolving component contained in the treatment liquid may not dissolve the object to be removed but may partially dissolve the surface layer 166 of the substrate W.

Furthermore, in the above embodiment, when the substrate processing of the above embodiment is performed after CMP, if the processing film 100 is formed, a gap G4 is formed between the processing film 100 and the pattern surface 165. However, between the processing film 100 and the pattern surface 165, the gap G4 does not need to be clearly formed to the extent that it can be confirmed by an analysis machine, as long as the surface layer 166 of the substrate W is dissolved into the processing film 100 by the dissolved components in the processing film 100 The degree of adhesion to the pattern surface 165 is reduced.

Similarly, the other gaps G1 to G3 do not need to be clearly formed to the extent that they can be confirmed by an analysis machine. That is, referring to FIG. 7B, the dissolved component in the treatment liquid only needs to dissolve the residue film 106 to the extent that the adhesion between the residue film 106 and the pattern surface 165 is reduced. Referring to FIG. 7D, the removing liquid only needs to be able to dissolve the low-solubility solid 111 to the extent that the adhesion between the treatment film 100 and the pattern surface 165 is reduced. Furthermore, referring to FIG. 8B, the dissolving component in the treatment liquid only needs to be able to dissolve the residue 113 and the surface layer 166 of the substrate W to the extent that the adhesion between the residue film 106 and the pattern surface 165 is reduced.

In addition, in the above-mentioned embodiment, the solute of the treatment liquid includes at least a soluble component, a high-soluble component, and a low-soluble component. However, it is also possible to use a treatment liquid that does not contain a high-solubility component but contains a low-solubility component and a soluble component as the solute. In this case, the treatment film 100 includes a low solubility solid 111 and a dissolved component solid 112. In this case, the treatment film 100 is removed from the upper surface of the substrate W by dissolving a part of the low solubility solid 111 by the removing liquid.

In addition, there are cases where, in the thinning step (step S3), the processing film 100 is formed by solvent evaporation when the liquid film 101 of the processing liquid is thinned. In this case, the solvent evaporation step (step S4) can be omitted. In this case, the processing film forming unit does not include the central nozzle 11 and the lower surface nozzle 12, and the processing film forming unit is composed of a substrate rotating unit (rotating motor 23). In addition, in the solvent evaporation step (step S4), only the heating step may be omitted, or only the gas supply step may be omitted.

Furthermore, in the above-mentioned substrate processing, the rinsing step (step S6) is performed after the removing step (step S5). However, the washing step can also be omitted. In detail, in the case where the removal liquid supplied to the substrate W in the removal step and the treatment film residue removal step (step S7) performed after the rinsing step are compatible, there is no need to perform Rinse step.

The embodiments of the present invention have been described in detail, but these are only specific examples used to clarify the technical content of the present invention. The present invention should not be limited to these specific examples for interpretation. Attached is the limitation of the scope of patent application.

This application corresponds to Japanese Patent Application No. 2019-122030 filed with the Japan Patent Office on June 28, 2019, and the entire disclosure of this application is incorporated herein by reference.

1: Substrate processing equipment 2: processing unit 3: Controller 3A: Processor 3B: Memory 4: chamber 5: Rotating chuck 6: Opposite member 6a: Opposite side 6b: Connecting hole 7: Handling the cup 9: The first moving nozzle 10: The second moving nozzle 11: Central nozzle 11a: Ejector 12: Nozzle on the lower surface 12a: Ejector 20: Chuck pin 21: Rotating base 21a: Through hole 22: Rotation axis 23: Rotating motor 30: shell 31: 1st tube 32: 2nd tube 33: third tube 36: The first nozzle moving unit 37: The second nozzle moving unit 40: Treatment liquid piping 41: Upper side removal fluid piping 42: Upper flushing fluid piping 43: Treatment membrane residue removal liquid piping 44: Gas piping 50: Treatment liquid valve 51: upper side removal valve 52: Upper flushing fluid valve 53: Treatment membrane residue removal valve 54: Gas valve 60: Hollow shaft 60a: internal space 61: Opposite member lifting unit 71: Guard 71A: The first shield 71B: 2nd shield 72: Cup 72A: 1st cup 72B: 2nd cup 73: Outer wall components 74: Shield lifting unit 80: Common piping 81: Lower flushing fluid piping 82: Lower side removal fluid piping 83: Heat medium piping 86: Lower flushing fluid valve 87: Lower side removal valve 88: Heat medium valve 100: Treatment membrane 101: Liquid film 103: residue 104: Slot 105: recess 106: Residual diaphragm 107: Through hole 110: Highly soluble solid 111: Low solubility solid 112: Dissolved component solids 113: dregs 160: bump pattern 161: Structure 161a: Surface 161b: Front face 161c: side 162: Concave 162a: bottom surface 165: pattern surface 166: Surface A1: Rotation axis C: Vehicle CR: Transport manipulator D: Orthogonal direction G1: gap G2: gap G3: gap G4: gap IR: Transfer robot L1: width L2: interval LP: Load port N: Normal direction T: thickness direction T1: Pattern height W: substrate

FIG. 1 is a schematic plan view showing the layout of a substrate processing apparatus according to an embodiment of the present invention. Fig. 2 is a schematic partial cross-sectional view showing a schematic configuration of a processing unit provided in the above-mentioned substrate processing apparatus. Fig. 3 is a block diagram showing the electrical configuration of the main part of the substrate processing apparatus. FIG. 4 is a flowchart for explaining an example of substrate processing performed by the above-mentioned substrate processing apparatus. FIG. 5A is a schematic diagram for explaining the processing liquid supply step (step S2) of the above-mentioned substrate processing. FIG. 5B is a schematic diagram for explaining the thinning step (step S3) of the above-mentioned substrate processing. FIG. 5C is a schematic diagram for explaining the solvent evaporation step (step S4) of the above-mentioned substrate processing. FIG. 5D is a schematic diagram for explaining the solvent evaporation step (step S4) of the above-mentioned substrate processing. FIG. 5E is a schematic diagram for explaining the removal step (step S5) of the above-mentioned substrate processing. FIG. 5F is a schematic diagram for explaining the condition of the washing step (step S6) of the above-mentioned substrate processing. FIG. 5G is a schematic diagram for explaining the process film residue removal step (step S7) of the above-mentioned substrate processing. FIG. 5H is a schematic diagram for explaining the spin drying step (step S8) of the above-mentioned substrate processing. 6 is a schematic cross-sectional view for explaining an example of the structure of the pattern surface of the substrate processed by the above-mentioned substrate processing apparatus. FIG. 7A is a schematic diagram for explaining the state of the surface of the substrate before the processing liquid supply step of the substrate processing when the substrate after the dry etching is used for the substrate processing. FIG. 7B is a schematic diagram for explaining the state of the surface of the substrate in the processing liquid supply step of the substrate processing when the substrate after the dry etching is used for the substrate processing. FIG. 7C is a schematic diagram for explaining the state of the surface of the substrate after the solvent evaporation step of the above-mentioned substrate treatment when the substrate after the dry etching is used for the above-mentioned substrate treatment. FIG. 7D is a schematic diagram for explaining the state of the surface of the substrate in the removal step of the above-mentioned substrate treatment when the substrate after the dry etching is used for the above-mentioned substrate treatment. FIG. 7E is a schematic diagram for explaining the state of the surface of the substrate in the removal step of the above-mentioned substrate treatment when the substrate after the dry etching is used for the above-mentioned substrate treatment. FIG. 8A is a schematic diagram for explaining the state of the surface of the substrate in the process liquid supply step of the substrate processing when the substrate after CMP is used for the substrate processing. FIG. 8B is a schematic diagram for explaining the state of the surface of the substrate in the processing liquid supply step of the substrate processing when the substrate after the CMP is used for the substrate processing. FIG. 8C is a schematic diagram for explaining the state of the surface of the substrate after the solvent evaporation step of the substrate treatment when the substrate after CMP is used for the substrate treatment. FIG. 8D is a schematic diagram for explaining the state of the surface of the substrate after the solvent evaporation step of the substrate processing when the substrate after CMP is used for the substrate processing. FIG. 8E is a schematic diagram for explaining the state of the surface of the substrate in the removal step of the substrate processing when the substrate after CMP is used for the substrate processing. FIG. 8F is a schematic diagram for explaining the state of the surface of the substrate in the removal step of the substrate processing when the substrate after CMP is used for the substrate processing.

103: residue

106: Residual diaphragm

165: pattern surface

166: Surface

G1: gap

N: Normal direction

W: substrate

Claims (20)

A substrate processing method, comprising: a processing liquid supply step, which supplies the processing liquid to the surface of a substrate; a processing film forming step, which solidifies or hardens the processing liquid on the surface of the substrate to form a substrate holding the substrate A treatment film for removing an object existing on the surface; and a removing step of removing the treatment film from the substrate while maintaining the treatment film with the removal object by supplying a removal liquid to the surface of the substrate Surface removal; the treatment liquid includes a dissolving component for dissolving at least one of the surface layer of the substrate and the object to be removed as a dissolution target, and the supplying step of the treatment liquid includes a dissolving step, and the dissolving step is supplied to the substrate by The dissolving component in the treatment solution on the surface locally dissolves the dissolution target, the dissolution target includes at least the removal target, the removal target includes a removal target film covering at least a part of the surface of the substrate, and the dissolution In the step, the removal target film is dissolved by the dissolving component in the treatment solution, thereby forming the film of the removal target film, and the treatment film formed in the process film forming step holds the film of the removal target film . A substrate processing method, which includes: The processing liquid supply step is to supply the processing liquid to the surface of the substrate; the processing film formation step is to solidify or harden the processing liquid on the surface of the substrate to form a removal target that maintains the presence of the surface of the substrate Film; and a removal step, which is by supplying a removal liquid to the surface of the substrate to remove the treatment film from the surface of the substrate in a state in which the treatment film retains the removal target; the treatment liquid includes making At least one of the surface layer of the substrate and the object to be removed serves as a dissolving component to dissolve the object, and the process liquid supply step includes a dissolving step, which is performed by the process liquid supplied to the surface of the substrate. The dissolving component partially dissolves the dissolution target, and in the dissolving step, the surface layer of the substrate is dissolved in the dissolving component in the treatment liquid, thereby separating the removal target from the surface of the substrate. The substrate processing method of claim 1 or 2, wherein the processing film forming step includes a step of curing or hardening the processing liquid in a state where the processing liquid has entered between the removal object and the surface of the substrate. The substrate processing method according to claim 1 or 2, wherein the processing film forming step includes a dissolution inhibiting step that inhibits the dissolution of the dissolution target by the dissolving component by curing or hardening the processing liquid . The substrate processing method of claim 4, wherein the above-mentioned dissolving object includes at least the above-mentioned substrate The surface layer, and the dissolution inhibiting step includes a step of dissolving the surface layer of the substrate by the dissolving component in the processing film near the contact interface between the processing film and the substrate. The substrate processing method according to claim 4, wherein the object to be dissolved includes at least the surface layer of the substrate, and the dissolution inhibiting step includes dissolving the surface layer of the substrate by using the dissolving component in the processing film. The step of forming a gap between the processing film and the surface of the above-mentioned substrate. The substrate processing method of claim 1 or 2, wherein the processing liquid has a solute and a solvent that dissolves the solute, and the solute has the above-mentioned dissolved components, highly soluble components, and is less soluble than the above-mentioned highly soluble components In the low solubility component of the removal liquid, the processing film forming step includes a step of forming the processing film having the high solubility component in a solid state, the low solubility component in a solid state, and the dissolved component in a solid state, and The removing step includes a step of selectively dissolving the highly soluble component in the solid state of the treatment film in the removing liquid. The substrate processing method of claim 1 or 2, wherein the removal object existing on the surface of the substrate is chemically bonded to the surface of the substrate. The substrate processing method of claim 1, wherein the removal target film is a residue generated by dry etching. The substrate processing method according to claim 8, wherein the object to be dissolved includes the surface layer of the substrate and the object to be removed, and the object to be removed is a residue generated by chemical mechanical polishing. A substrate processing apparatus comprising: a processing liquid supply unit that supplies the processing liquid to the surface of a substrate; a processing film forming unit that solidifies or hardens the processing liquid on the surface of the substrate to form a surface that maintains the presence of the substrate The treatment film for removing the object; a removal liquid supply unit that removes the treatment film from the surface of the substrate by supplying a removal liquid to the surface of the substrate; and a controller that supplies the treatment liquid to the treatment liquid supply unit and the treatment The film forming unit and the removal liquid supply unit are controlled; the controller is programmed to perform the following steps: a processing liquid supply step, which supplies the processing liquid from the processing liquid supply unit toward the surface of the substrate; a processing film formation step, by The processing film forming unit solidifies or hardens the processing liquid on the surface of the substrate to form the processing film on the upper surface of the substrate; and a removing step, by supplying the removal liquid supply unit toward the surface of the substrate A removal liquid for removing the treatment film from the surface of the substrate while maintaining the treatment film with the removal object; the treatment liquid contains at least one of the surface layer of the substrate and the removal object as a dissolution object The dissolved component of the substance, The controller is programmed to perform a dissolving step in the processing liquid supply step. The dissolving step is to partially dissolve the dissolution target by the dissolving component in the processing liquid supplied to the surface of the substrate, and the dissolution target The object includes at least the object to be removed, and the object to be removed includes a removal object film covering at least a part of the surface of the substrate, and in the dissolving step, the removal object film is dissolved by the dissolved component in the treatment solution to form The film of the removal target film, and the process film formed in the process film forming step holds the film of the removal target film. A substrate processing apparatus comprising: a processing liquid supply unit that supplies the processing liquid to the surface of a substrate; a processing film forming unit that solidifies or hardens the processing liquid on the surface of the substrate to form a surface that maintains the presence of the substrate The treatment film for removing the object; a removal liquid supply unit that removes the treatment film from the surface of the substrate by supplying a removal liquid to the surface of the substrate; and a controller that supplies the treatment liquid to the treatment liquid supply unit and the treatment The film forming unit and the removal liquid supply unit are controlled; the controller is programmed to perform the following steps: a processing liquid supply step, which supplies the processing liquid from the processing liquid supply unit toward the surface of the substrate; a processing film formation step, by The processing film forming unit solidifies or hardens the processing liquid on the surface of the substrate, and forms the processing film on the upper surface of the substrate; and the removing step, by supplying the removing liquid from the The unit supplies the removal liquid toward the surface of the substrate, and removes the treatment film from the surface of the substrate while keeping the removal target in the treatment film; the treatment liquid includes the surface layer of the substrate and the removal target At least one of the substances is used as the dissolving component of the dissolving target, and the controller is programmed to execute the dissolving step in the processing liquid supply step by the processing liquid supplied to the surface of the substrate. The dissolving component partially dissolves the dissolution target, and in the dissolving step, the surface layer of the substrate is dissolved in the dissolving component in the treatment liquid, thereby separating the removal target from the surface of the substrate. The substrate processing apparatus of claim 11 or 12, wherein the controller is programmed to perform the processing in a state in which the processing liquid has entered between the removal object and the surface of the substrate in the processing film forming step Liquid solidifies or hardens. The substrate processing apparatus of claim 11 or 12, wherein the controller is programmed to perform a dissolution inhibiting step in the process film forming step, and the dissolution inhibiting step suppresses the utilization of the dissolved component by curing or hardening the process liquid Dissolve the above-mentioned object to be dissolved. The substrate processing apparatus of claim 14, wherein the object to be dissolved includes at least the surface layer of the substrate, and the controller is programmed to execute the vicinity of the contact interface between the processing film and the substrate in the dissolution inhibiting step A step of treating the above-mentioned dissolved components in the film to dissolve the above-mentioned surface layer of the above-mentioned substrate. The substrate processing apparatus of claim 14, wherein the dissolution target includes at least the surface layer of the substrate, and the controller is programmed to execute the dissolution suppression step by using the dissolution component in the processing film to make the substrate The step of dissolving the surface layer to form a gap between the processing film and the surface of the substrate. The substrate processing apparatus of claim 11 or 12, wherein the processing liquid has a solute and a solvent that dissolves the solute, and the solute has the above-mentioned soluble component, a highly soluble component, and is less soluble than the above-mentioned highly soluble component In the low solubility component of the removal liquid, and the controller is programmed to form the high solubility component in the solid state, the low solubility component in the solid state, and the dissolution in the solid state in the process film forming step In the above-mentioned treatment film of components, in the above-mentioned removal step, the solid state of the above-mentioned highly soluble component in the above-mentioned treatment film is selectively dissolved in the above-mentioned removal liquid. The substrate processing apparatus of claim 11 or 12, wherein the removal target object existing on the surface of the substrate is chemically bonded to the surface of the substrate. The substrate processing apparatus of claim 11, wherein the removal target film is a residue generated by dry etching. The substrate processing apparatus of claim 18, wherein the object to be dissolved includes the substrate The surface layer and the removal object, and the removal object is a residue generated by chemical mechanical polishing.

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